Composition having permitivity being radiation-sensitively changeable and method for forming permitivity pattern

ABSTRACT

A radiation sensitive dielectric constant changing composition comprising (A) a decomposable compound, (B) a nondecomposable compound, (C) a radiation sensitive decomposer and (D) a stabilizer.  
     The composition allows its dielectric constant to be changed by a simple method, has a sufficiently large difference between its changed dielectric constant and its original dielectric constant and can provide a dielectric constant pattern and an optical material which are stable regardless of their use conditions.

FIELD OF THE INVENTION

[0001] The present invention relates to a radiation sensitive dielectricconstant changing composition, a method of forming a dielectric constantpattern, a dielectric constant pattern and a device having a dielectricconstant pattern. More specifically, it relates to a novel radiationsensitive dielectric constant changing composition which can provide adielectric constant pattern for use as an insulating material or acapacitor for circuit boards, a method of forming a dielectric constantpattern, a dielectric constant pattern and a device having a dielectricconstant pattern.

DESCRIPTION OF THE PRIOR ART

[0002] Technical development for reducing the length of wiring, thedielectric constant of an interlayer film and the length of a gate isnow under way in order to increase the speed of a semiconductor. Thefield of packaging technology for creating a system usable state whileretaining the performance of a semiconductor is far behind the abovedevelopment. Packaging structures are now being reviewed to catch upwith the above development. For example, attempts are being made toreduce the length of wiring and the dielectric constant of an interlayerfilm in the field of packaging technology.

[0003] In conventional packaging technology, the performance of a memoryIC is maintained by placing a path capacitor or input/output capacitornear an IC terminal. However, there arises the need of placing theseelements near an element to increase the speed, and studies on how tobring a passive element, which has been positioned away from an IC, asclose to the IC as possible to reduce the length of wiring so as toincrease the speed are now under way. As a result, attention is now paidto a substrate structure such as “embedded passive”.

[0004] In the above packaging technology, in order to form adistribution having a difference between two different dielectricconstants, one material is first formed, followed by the deposition ofanother material having a different dielectric constant on the entiresurface of the above material. Thereafter, an unrequired depositedportion is removed by etching after patterning with a photosensitivematerial. Since this method has a large number of steps and the obtainedfilm is apt to greatly vary in thickness, a material which provides afilm having high uniformity in thickness is desirably used as thematerial on which another material is deposited.

[0005] As the integration becomes higher, a lower dielectric constantmaterial is needed for an interlayer insulating film used to prevent adelay caused by cross talk between wirings in the assembly of a highlyintergrated circuit. To this end, studies on the reduction of dielectricconstant using organic and inorganic materials are now under way. As oneof the studies, the reduction of dielectric constant using porousmaterials has been reported in Mat. Res. Soc. Symp. Proc., Vol. 511, 105(1998); Electrochemical and Solid-State letters, Vol. 2, 77 (1999);Proc. DUMIC Santa Clara, 25 (1998); collection of drafts for the 61stlecture meeting of the Applied Physics Society, 4a-P4-20 (2000);collection of drafts for the 61st lecture meeting of the Applied PhysicsSociety, 4a-P4-27 (2000); Proc. of the 2000 IITC, 143 (2000) and thelike. A reduction in density by using a porous material makes itpossible to form a film having a dielectric constant of 2 or less.However, since a reduction in the density of a film has a directinfluence on the reduction of the strength of the film although itreduces the dielectric constant of the film, the development of aninterlayer insulating film having higher strength than a conventionalinterlayer insulating film is desired.

[0006] Meanwhile, studies on the reduction of the capacity of wiring byemploying a hollow structure containing air which has the lowestdielectric constant as the structure of a highly integrated circuit havebeen reported by JP-A 63-268254 (the term “JP-A” as used herein means an“unexamined published Japanese patent application”); Microprocessorreport, August 4, 14 (1997); Symp. On VLSI Technology, 82 (1996); DUMICConference, 139 (1997); IEEE Electron Device Letters, Vol. 19, No. 1, 16(1998) and the like. However, this hollow structure involves manyproblems in its process, for example, extremely high accuracy requiredfor assembly and therefore is not implemented yet.

SUMMARY OF THE INVENTION

[0007] The present invention has been made in view of the abovesituation in the prior art.

[0008] That is, it is an object of the present invention to provide aradiation sensitive dielectric constant changing composition whosedielectric constant can be changed by a simple method and which has asufficiently large difference between its changed dielectric constantand its original dielectric constant and which can provide a dielectricconstant pattern which is stable regardless of its use conditions.

[0009] It is another object of the present invention to provide aradiation sensitive dielectric constant changing composition whichprovides a dielectric constant pattern having a large number of poresformed by exposure to radiation and maintained stably, and having highstrength in spite of having the large number of pores.

[0010] It is still another object of the present invention to provide amethod of forming a dielectric constant pattern from the abovecomposition of the present invention.

[0011] It is a further object of the present invention to provide adielectric constant pattern produced by the above method of the presentinvention or a device having the dielectric constant pattern.

[0012] Other objects and advantages of the present invention will becomeapparent from the following description.

[0013] According to the present invention, firstly, the above objectsand advantages of the present invention are attained by a radiationsensitive dielectric constant changing composition comprising (A) adecomposable compound, (B) a nondecomposable compound, (C) a radiationsensitive decomposer and (D) a stabilizer.

[0014] According to the present invention, secondly, the above objectsand advantages of the present invention are attained by a method offorming a dielectric constant pattern, comprising the steps of exposinga radiation sensitive dielectric constant changing compositioncomprising (A) a decomposable compound, (B) a nondecomposable compound,(C) a radiation sensitive decomposer and (D) a stabilizer to radiationand heating it to react the stabilizer (D) with the decomposablecompound (A).

[0015] According to the present invention, thirdly, the above objectsand advantages of the present invention are attained by a method offorming a dielectric constant pattern, comprising the steps of exposinga dielectric constant changing material comprising (A) a decomposablecompound, (B) a nondecomposable compound and (C) a radiation sensitivedecomposer to radiation and treating it with (D) a stabilizer.

[0016] According to the present invention, in the fourth place, theabove objects and advantages of the present invention are attained by amethod of forming a dielectric constant pattern, comprising the steps ofexposing a dielectric constant changing material comprising (A) adecomposable compound, (B) a nondecomposable compound and (C) aradiation sensitive decomposer to radiation through a pattern mask andheating it to decompose the decomposable compound in an unexposedportion.

[0017] According to the present invention, in the fifth place, the aboveobjects and advantages of the present invention are attained by adielectric constant pattern formed by the above method of forming adielectric constant pattern.

[0018] According to the present invention, in the sixth place, the aboveobjects and advantages of the present invention are attained by a devicehaving the above dielectric constant pattern.

[0019] In the present invention, the term “dielectric constant pattern”as used herein means a dielectric constant distribution materialconsisting of regions having different dielectric constants.

[0020] Each of the components of the dielectric constant changingmaterial used in the method of forming a dielectric constant pattern ofthe present invention will be described in detail hereinunder.

[0021] (A) Decomposable Compound

[0022] The decomposable compound (A) used in the present invention canbe an acid decomposable compound or a base decomposable compound.

[0023] The acid decomposable compound is selected from compounds havingat least one of structures represented by the following formulas (1) to(6) and (10). These compounds may be used alone or in combination of twoor more.

[0024] (In the formula (1), R¹ is an alkylene group,alkylene-arylene-alkylene group or arylene group, and R² is an alkylenegroup, alkylene-arylene-alkylene group, arylene group, alkylsilylenegroup or alkylgermylene group.)

[0025] (In the formula (2), M is Si or Ge, R³ is an alkylene group,alkylene-arylene-alkylene group, arylene group, alkylsilylene group oralkylgermylene group, R⁴ is an oxygen atom, alkylene group,alkylene-arylene-alkylene group, arylene group or single bond, R⁵, R⁶,R⁷ and R⁸ are each independently a hydrogen atom, alkyl group, arylgroup, alkoxy group or thioalkyl group, and m is an integer of 0 to 2.)

[0026] (In the formula (3), R⁹ and R¹⁰ are each independently analkylene group, alkylene-arylene-alkylene group, arylene group,alkylsilylene group or alkylgermylene group.)

[0027] (In the formula (4), R¹¹ is an oxyalkylene group or single bond,and R¹² is a hydrogen atom, alkyl group, alkylene-arylene-alkylene groupor aryl group.)

[0028] (In the formula (5), R¹³ is a hydrogen atom, alkyl group or arylgroup.)

[0029] (In the formula (6), R¹⁴ is an alkylene group or a structurerepresented by the following formula (7), (8) or (9).)

[0030] (In the formula (7), R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are each independentlya hydrogen atom, chain alkyl group having 1 to 6 carbon atoms, chlorineatom, bromine atom, iodine atom, hydroxyl group, mercapto group,carboxyl group, alkoxyl group having 1 to 6 carbon atoms, alkylthiogroup having 1 to 6 carbon atoms, haloalkyl group having 1 to 6 carbonatoms, haloalkoxyl group having 1 to 6 carbon atoms, haloalkylthio grouphaving 1 to 6 carbon atoms, hydroxyalkyl group having 1 to 6 carbonatoms, mercaptoalkyl group having 1 to 6 carbon atoms, hydroxyalkoxylgroup having 1 to 6 carbon atoms, mercaptoalkylthio group having 1 to 6carbon atoms, aryl group having 6 to 10 carbon atoms or aralkyl grouphaving 7 to 11 carbon atoms.)

—O—R¹⁹—O—  (8)

[0031] (In the formula (8), R¹⁹ is an alkylene group.)

—NH—R²⁰—NH—  (9)

[0032] (In the formula (9), R²⁰ is an alkylene group.)

[0033] (In the formula (10), R²¹ is an alkylene group,alkylene-arylene-alkylene group or arylene group.)

[0034] The acid decomposable compounds having structures represented bythe above formulas (1) to (6) and (10) are decomposed by an acidgenerated from a radiation sensitive acid decomposer upon exposure toradiation. A low-molecular weight compound formed by decomposition is acompound such as a carbonic acid gas which is gaseous at normaltemperature or a compound which can evaporate or sublime as a gas whenit is treated at an increased temperature. After the dissipation of thegas, pores are formed.

[0035] As the acid decomposable compound (A) may be used (i) a phenolicresin having at least two phenolic hydroxyl groups and at least twophenyl groups in the molecule, at least one of the phenolic hydroxylgroups forming a naphthoquinonediazidosulfonyl ester group such as1,2-naphthoquinonediazido-5-sulfonyl ester group, (ii) a novolak resinhaving at least one phenolic hydroxyl group forming anaphthoquinonediazidosulfonyl ester group such as1,2-naphthoquinonediazido-5-sulfonyl ester group, (iii) a phenolic resinhaving at least two phenolic hydroxyl groups and at least two phenylgroup in the molecule, at least one of the phenolic hydroxyl groupsbeing protected by an acid decomposable protective group, (iv) a novolakresin having at least one phenolic hydroxyl group protected by an aciddecomposable protective group, and (v) a carboxyl group-containing resinhaving at least one carboxyl group protected by an acid decomposableprotective group.

[0036] These resins (i) to (v) may be used alone or in combination oftwo or more.

[0037] The above acid decomposable compounds (i) to (v) are decomposedby an acid generated from a radiation sensitive acid decomposer uponexposure to radiation to form a phenolic resin, novolak resin orcarboxyl group-containing resin all of which are alkali-soluble resins.These formed alkali-soluble resins are removed by extraction with analkali aqueous solution and pores are formed after extraction.Therefore, since extraction with an alkali aqueous solution is carriedout when any one of the acid decomposable compounds (i) to (v) is usedas the component (A), a polymer insoluble in an alkali aqueous solution,e.g., a polymer having no carboxyl group or phenolic hydroxyl group ispreferably used as the component (B), namely, an acid nondecomposablecompound.

[0038] The base decomposable compound is selected from compounds havingat least one of structures represented by the following formulas (11) to(13) and (14). These compounds may be used alone or in combination oftwo or more.

[0039] (In the formula (11), R²² is an alkylene group, aralkylene groupor arylene group, R²³ is an alkylene group, aralkylene group, arylenegroup, alkylene-arylene-alkylene group, alkylsilylene group oralkylgermylene group, R²⁴, R²⁵, R²⁶ and R²⁷ are each independently ahydrogen atom, alkyl group, aryl group, alkoxyl group or thioalkylgroup, and i and j are each independently 0 or 1.)

[0040] (In the formula (12), R²⁸ is an alkylene group, aralkylene groupor arylene group, and R²⁹ is an alkylene group, aralkylene group,arylene group, alkylene-arylene-alkylene group, alkylsilylene group oralkylgermylene group.)

[0041] (In the formula (13), R³⁰ and R³¹ are each independently analkylene group, aralkylene group, arylene group,alkylene-arylene-alkylene group, alkylsilylene group or alkylgermylenegroup.)

[0042] (In the formula (14), R³² and R³³ are each independently analkylene group, aralkylene group, arylene group,alkylene-arylene-alkylene group, alkylsilylene group or alkylgermylenegroup.)

[0043] All the above alkylene-arylene-alkylene groups each independentlyhave a structure represented by the following formula (15) or (16):

[0044] (In the formula (15), R³⁴, R³⁵, R³⁶ and R³⁷ are eachindependently a hydrogen atom, chain alkyl group having 1 to 6 carbonatoms or aryl group having 6 to 10 carbon atoms, and R³⁸, R³⁹, R⁴⁰ andR⁴¹ are each independently a hydrogen atom, chlorine atom, bromine atom,hydroxyl group, mercapto group, alkoxyl group, thioalkyl group,alkylester group, alkylthioester group, aryl group, cyano group or nitrogroup.)

[0045] (In the formula (16), R⁴², R⁴³, R⁴⁴ and R⁴⁵ are eachindependently a hydrogen atom, chain alkyl group having 1 to 6 carbonatoms or aryl group having 6 to 10 carbon atoms, R⁴⁶, R⁴⁷, R⁴⁸, R⁴⁹,R⁵⁰, R⁵¹, R⁵² and R⁵³ are each independently a hydrogen atom, chlorineatom, bromine atom, hydroxyl group, mercapto group, alkoxyl group,thioalkyl group, alkylester group, alkylthioester group, aryl group,cyano group or nitro group, and A¹ is —S—, —O—, —SO₂—, —CO—, —COO—,—OCOO—, —CH₂— or —C(R⁵⁴)₂— (R⁵⁴ is a chain alkyl group having 1 to 6carbon atoms.)

[0046] All the above arylene groups each independently have a structurerepresented by the following formula (17):

[0047] wherein R⁵⁵ to R⁶² are each independently a hydrogen atom,chlorine atom, bromine atom, hydroxyl group, mercapto group, alkoxylgroup, thioalkyl group, alkylester group, alkylthioester group, arylgroup, cyano group or nitro group, and A² is —S—, —O—,—SO₂—, —CO—,—COO—, —OCOO—, —CH₂— or —C(R⁶³)₂— (R⁶³ is a chain alkyl group having 1to 6 carbon atoms).

[0048] All the above alkylsilylene groups each independently have astructure represented by the following formula (18):

[0049] wherein R⁶⁴, R⁶⁵, R⁶⁶ and R⁶⁷ are each independently a hydrogenatom, chain alkyl group having 1 to 6 carbon atoms or aryl group having6 to 10 carbon atoms, A³ is —O—, alkylene group or arylene group, and ais an integer of 0 or 1.

[0050] All the above alkylgermylene groups each independently have astructure represented by the following formula (19):

[0051] wherein R⁶⁸, R⁶⁹, R⁷⁰ and R⁷¹ are each independently a hydrogenatom, chain alkyl group having 1 to 6 carbon atoms or aryl group having6 to 10 carbon atoms, A⁴ is —O—, alkylene group or arylene group, and bis an integer of 0 or 1.

[0052] All the above alkylene groups in the above formulas (18) and (19)are each independently and preferably a linear, branched or cyclicalkylene group having 1 to 10 carbon atoms such as methylene,1,2-ethylene, 1,3-trimethylene or 1,10-decamethylene, and a hydrogenatom contained in the above groups may be substituted by a chlorineatom, bromine atom, hydroxyl group, mercapto group, alkoxyl group,thioalkyl group, alkylester group, alkylthioester group, aryl group orcyano group.

[0053] All the above alkyl groups and alkyl groups contained in theabove alkoxyl groups, thioalkyl groups, alkylester groups andalkylthioester groups are each independently and preferably a linear,branched or cyclic alkyl group having 1 to 10 carbon atoms, and ahydrogen atom contained in the above groups may be substituted by achlorine atom, bromine atom, hydroxyl group, mercapto group, alkoxylgroup, thioalkyl group, alkylester group, alkylthioester group, arylgroup or cyano group.

[0054] All the above aryl groups are each independently a phenyl group,naphthyl group, anthracenyl group or biphenyl group, and a hydrogen atomcontained in the above groups may be substituted by a chlorine atom,bromine atom, hydroxyl group, mercapto group, alkoxyl group, thioalkylgroup, alkylester group, alkylthioester group, cyano group or nitrogroup.

[0055] Methods of producing acid decomposable compounds havingstructures represented by the above formulas (1) to (6) and (10) as arecurring unit, for example, in the present invention are already known.

[0056] Methods of producing a compound having a structure represented bythe above formula (1) are disclosed by Polymer Bull., 1. 199 (1978),JP-A 62-136638, EP 225,454, U.S. Pat. No. 806,597, JP-A 4-303843, JP-A7-56354 and the like.

[0057] Methods of producing a compound having a structure represented bythe above formula (2) are disclosed by Macromolecules 29, 5529 (1996),Polymer 17, 1086 (1976), JP-A 60-37549 and the like.

[0058] Methods of producing a compound having a structure represented bythe above formula (3) are disclosed by Electrochem. Soc., Solid StateSci. Technol., 133(1) 181 (1986); J. Imaging Sci., 30(2)59 (1986);Macromol. Chem., Rapid Commun., 7, 121 (1986) and the like.

[0059] Methods of producing a compound having a structure represented bythe above formula (4) are disclosed by U.S. Pat. No. 3,894,253, JP-A62-190211, JP-A 2-146544, Macromol. Chem., 23, 16 (1957); JP-A 63-97945,Polymer Sci., A-1, 8, 2375 (1970); U.S. Pat. No. 4,247,611, EP 41,657,JP-A 57-31674, JP-A 64-3647, JP-A 56-17345 and the like.

[0060] Methods of producing a compound having a structure represented bythe above formula (5) are disclosed by Prepr. Eur. Disc Meet. PolymerSci., Strasbourg, p.106 (1978), Macromol. Chem., 179, 1689 (1978) andthe like.

[0061] Methods of producing a compound having a structure represented bythe above formula (6) are disclosed by U.S. Pat. No. 3,894,253, U.S.Pat. No. 3,940,507, JP-A 62-190211 and the like.

[0062] Methods of producing a compound having a structure represented bythe above formula (10) are disclosed by J. Am. Chem. Soc., 54, 1579(1932); J. Polym. Sci., 29, 343 (1958); J. Polym. Sci., Part A, Polym.Chem., 25, 3373 (1958); Macromolecules, 25, 12, (1992); Macromolecules,20, 705, (1997); Macromolecules, 21, 1925, (1998); Macromol. Chem.,Rapid Commun., 11, 83 (1990) and the like.

[0063] Methods of producing base decomposable compounds havingstructures represented by the above formulas (11) to (14) as a recurringunit are also known.

[0064] Methods of producing a compound having a structure represented bythe above formula (11) are disclosed by Macromol. Chem., Rapid Commun.,5, 151 (1984); Macromol. Chem., 189, 2229 (1988); Macromol. Chem., 187,2525 (1986); Polym. J., 22, 803 (1990) and the like.

[0065] Methods of producing a compound having a structure represented bythe above formula (12) are disclosed by J. Polym. Sci., 47, 1523 (1993);J. Appl. Polym. Sci., 35, 85 (1985); J. Polym. Sci., Polym. Chem. Ed.,22, 1579 (1984); J. Polym. Sci., Polym. Chem. Ed., 14, 655 (1976); J.Polym. Sci., Polym. Chem. Ed., 17, 2429 (1979) and the like.

[0066] Methods of producing a compound having a structure represented bythe above formula (13) are disclosed by J. Macromol. Sci. -Chem., A9,1265 (1975) and the like.

[0067] Methods of producing a compound having a structure represented bythe above formula (14) are disclosed by Polym. Bull., 14, 85 (1985);Macromol. Chem., 189, 1323 (1988) and the like.

[0068] The number of recurring units of the decomposable compound (A) ispreferably 1 to 5,000.

[0069] (B) Nondecomposable Compound

[0070] The nondecomposable compound (B) used in the present invention isa material stable to an acid or base. The dielectric constant of thecomponent (B) can be set or adjusted to a preferred value according toapplication purpose.

[0071] The nondecomposable compound (B) is, for example, an acrylicresin, urethane-based resin, polyester-based resin, polycarbonate-basedresin, norbornene-based resin, styrene-based resin, polyethersulfone-based resin, silicon resin, polyamide resin, polyimide resin,polysiloxane-based resin, fluorine-based resin, polybutadiene-basedresin, vinylether-based resin, vinylester-based resin, polyarylether-based polymer, polyarylene-based polymer, polyamide-based polymer,polyimide-based polymer, polyethylene, polyproylene, polycarbonate-basedpolymer, polyarylate-based polymer, polyamide-based polymer, polyamideimide-based polymer, polysulfone-based polymer, polyether sulfone-basedpolymer, polyether ketone-based polymer, polyphenylene sulfide-basedpolymer, polyether imide-based polymer, polyamide imide-based polymer,polyester imide-based polymer, modified polyphenylene oxide-basedpolymer, polybenzooxazole-based polymer, polyacrylic acid-based polymer,maleimide-based polymer, quinoline-based resin, benzocyclobutene-basedresin, Parylene-based resin, epoxy resin, acrylic resin, novolak resin,styrene resin, phenolic resin, urea resin, isocyanate-based resin,bismaleimide resin, cyanate resin, hydrocarbon-based resin, nanofoams,organic SOG, thermosetting PPE resin and what are obtained bysubstituting some or all of the hydrogen atoms thereof by a fluorineatom, such as silicon fluoride-based polymer, cycloperfluorocarbonpolymer, fluorocarbon, perfluorovinyl ether, Teflon (registered) orfullerene fluoride.

[0072] Specific examples of the nondecomposable compound (B) include thefollowing polymers: polyvinylidene fluoride, polydimethylsiloxane,polytrifluoroethyl methacrylate, polyoxypropylene, polyvinylisobutylether, polyvinylethyl ether, polyoxyethylene, polyvinylbutyl ether,polyvinylpentyl ether, polyvinylhexyl ether, poly(4-methyl-1-pentene),cellulose acetate butyrate, poly(4-fluoro-2-trifluoromethylstyrene),polyvinyloctyl ether, poly(vinyl 2-ethylhexyl ether), polyvinyldecylether, poly(2-methoxyethyl acrylate), polybutyl acrylate, poly(t-butylmethacrylate), polyvinyldodecyl ether, poly(3-ethoxypropyl acrylate),polyoxycarbonyl tetramethylene, polyvinyl propionate, polyvinyl acetate,polyvinylmethyl ether, polyethyl acrylate, ethylene-vinyl acetatecopolymer, (80% to 20% of vinylacetate)cellulose propionate, celluloseacetate propionate, benzyl cellulose, phenol-formaldehyde resin,cellulose triacetate, polyvinylmethyl ether (isotactic),poly(3-methoxypropyl acrylate), poly(2-ethoxyethyl acrylate), polymethylacrylate, polyisopropyl methacrylate, poly(1-decene), polypropylene(atactic, density of 0.8575 g/cm³), poly(vinyl sec-butyl ether)(isotactic), polydodecyl methacrylate, polyoxyethylene oxysuccinoyl,(polyethylene succinate) polytetradecyl methacrylate, ethylene-propylenecopolymer (EPR-rubber), polyhexadecyl methacrylate, polyvinyl formate,poly(2-fluoroethyl methacrylate), polyisobutyl methacrylate, ethylcellulose, polyvinyl acetal, cellulose acetate, cellulose tripropionate,polyoxymethylene, polyvinyl butyral, poly(n-hexyl methacrylate),poly(n-butyl methacrylate), polyethylidene dimethacrylate,poly(2-ethoxyethyl methacrylate), polyoxyethylene oxymaleoyl,(polyethylene maleate) poly(n-propyl methacrylate),poly(3,3,5-trimethylcyclohexyl methacrylate), polyethyl methacrylate,poly(2-nitro-2-methylpropyl methacrylate), polytriethylcarbinylmethacrylate, poly(1,1-diethylpropyl methacrylate), polymethylmethacrylate, poly(2-decyl-1,3-butadiene), polyvinyl alcohol, polyethylglycolate methacrylate, poly(3-methylcyclohexyl methacrylate),poly(cyclohexyl α-ethoxyacrylate), methyl cellulose (low viscosity),poly(4-methylcyclohexyl methacrylate), polydecamethylene glycoldimethacrylate, polyurethane, poly(1,2-butadiene), polyvinyl formal,poly(2-bromo-4-trifluoromethylstyrene), cellulose nitrate,poly(sec-butyl α-chloroacrylate), poly(2-heptyl-1,3-butadiene),poly(ethyl α-chloroacrylate), poly(2-isopropyl-1,3-butadiene),poly(2-methylcyclohexyl methacrylate), polypropylene (density of 0.9075g/cm³), polyisobutene, polybornyl methacrylate,poly(2-t-butyl-1,3-butadiene), polyethylene glycol dimethacrylate,polycyclohexyl methacrylate, poly(cyclohexanediol-1,4-dimethacrylate),butyl rubber (unvulcanized), polytetrahydrofurfuryl methacrylate),guttapercha (β), polyethylene ionomer, polyoxyethylene (high molecularweight), polyethylene (density of 0.914 g/cm³), (density of 0.94 to0.945 g/cm³), (density of 0.965 g/cm³), poly(1-methylcyclohexylmethacrylate), poly(2-hydroxyethyl methacrylate), polyvinylchloroacetate, polybutene (isotactic), polyvinyl methacrylate,poly(N-butyl-methacrylamide), guttapercha (α), terpene resin,poly(1,3-butadiene), shellac, poly(methyl α-chloroacrylate),poly(2-chloroethyl methacrylate), poly(2-diethylaminoethylmethacrylate), poly(2-chlorocyclohexyl methacrylate),poly(1,3-butadiene) (35% of cis-form; 56% of trans-form 1.5180; 7% of1,2-addition), natural rubber, polyallyl methacrylate, polyvinylchloride+40% of dioctyl phthalate, polyacrylonitrile,polymethacrylonitrile, poly(1,3-butadiene) (rich with cis type),butadiene-acrylonitrile copolymer, polymethyl isopropenyl ketone,polyisoprene, polyester resin rigid (about 50% of styrene),poly(N-(2-methoxyethyl)methacrylamide), poly(2,3-dimethylbutadiene)(methyl rubber), vinyl chloride-vinyl acetate copolymer (95/5 to 90/10),polyacrylic acid, poly(1,3-dichloropropyl methacrylate),poly(2-chloro-1-(chloromethyl)ethyl methacrylate), polyacrolein,poly(1-vinyl-2-pyrrolidone), hydrochlorinated rubber, nylon 6; nylon6,6; nylon 6,10 (molded product), butadiene-styrene copolymer (about 30%of styrene), poly(cyclohexyl-α-chloroacrylate) block copolymer,poly(2-chloroethyl-α-chloroacrylate), butadiene-styrene copolymer (about75/25), poly(2-aminoethyl methacrylate), polyfurfuryl methacrylate,polybutylmercaptyl methacrylate, poly(1-phenyl-n-amyl methacrylate),poly(N-methyl-methacrylamide), cellulose, polyvinyl chloride, ureaformaldehyde resin, poly(sec-butyl α-bromoacrylate), poly(cyclohexylα-bromoacrylate), poly(2-bromoethyl methacrylate), polydihydroabieticacid, polyabietic acid, polyethylmercaptyl methacrylate,poly(N-allylmethacrylamide), poly(1-phenylethyl methacrylate),polyvinylfuran, poly(2-vinyltetrahydrofuran), poly(vinylchloride)+40% oftricresyl phosphate, poly(p-methoxybenzyl methacrylate), polyisopropylmethacrylate, poly(p-isopropylstyrene), polychloroprene,poly(oxyethylene-α-benzoate-ω-methacrylate), poly(p,p′-xylylenyldimethacrylate), poly(1-phenylallyl methacrylate),poly(p-cyclohexylphenyl methacrylate), poly(2-phenylethyl methacrylate),poly(oxycarbonyloxy-1,4-phenylene-1-propyl),poly(1-(o-chlorophenyl)ethylmethacrylate), styrene-maleic anhydridecopolymer, poly(1-phenylcyclohexyl methacrylate),poly(oxycarbonyloxy-1,4-phenylene-1,3-dimethylbutylidene-1,4-phenylene),poly(methyl α-bromoacrylate), polybenzyl methacrylate,poly(2-(phenylsulfonyl)ethyl methacrylate), poly(m-cresyl methacrylate),styrene-acrylonitrile copolymer (about 75/25),poly(oxycarbonyloxy-1,4-phenylene isobutylidene-1,4-phenylene),poly(o-methoxyphenyl methacrylate), polyphenyl methacrylate,poly(o-cresyl methacrylate), polydiallyl phthalate,poly(2,3-dibromopropyl methacrylate),poly(oxycarbonyloxy-1,4-phenylene-1-methyl-butylidene-1,4-phenylene),poly(oxy-2,6-dimethylphenylene), polyoxyethylene oxyterephthaloyl(amorphous), polyethylene terephthalate, polyvinyl benzoate,poly(oxycarbonyloxy-1,4-phenylenebutylidene-1,4-phenylene),poly(1,2-diphenylethyl methacrylate), poly(o-chlorobenzyl methacrylate),poly(oxycarbonyloxy-1,4-phenylene-sec-butylidene-1,4-phenylene),polyoxypentaerythritoloxyphthaloyl, poly(m-nitrobenzyl methacrylate),poly(oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene),poly(N-(2-phenylethyl)methacrylamide), poly(4-methoxy-2-methylstyrene),poly(o-methylstyrene), polystyrene,poly(oxycarbonyloxy-1,4-phenylenecyclohexylidene-1,4-phenylene),poly(o-methoxystyrene), polydiphenylmethyl methacrylate,poly(oxycarbonyloxy-1,4-phenyleneethylidene-1,4-phenylene),poly(p-bromophenyl methacrylate), poly(N-benzylmethacrylamide),poly(p-methoxystyrene), polyvinylidene chloride, polysulfide(“Thiokol”), poly(o-chlorodiphenylmethyl methacrylate),poly(oxycarbonyloxy-1,4-(2,6-dichloro)phenyleneisopropylidene-1,4-(2,6-dichloro)phenylene),poly(oxycarbonyloxybis(1,4-(3,5-dichlorophenylene)))polypentachlorophenyl methacrylate, poly(o-chlorostyrene), poly(phenylα-bromoacrylate), poly(p-divinylbenzene), poly(N-vinylphthalimide),poly(2,6-dichlorostyrene), poly(β-naphthyl methacrylate),poly(α-naphthylcarbinyl methacrylate), polysulfone,poly(2-vinylthiophene), poly(α-naphthyl methacrylate),poly(oxycarbonyloxy-1,4-phenylenediphenyl-methylene-1,4-phenylene),polyvinylphenyl sulfide, butylphenol formaldehyde resin,urea-thiourea-formaldehyde resin, polyvinyl naphthalene, polyvinylcarbazole, naphthalene-formaldehyde resin, phenol-formaldehyde resin andpolypentabromophenyl methacrylate.

[0073] As the component (B) used in the present invention may be used ahydrolyzate of at least one compound selected from the group consistingof a metal alkoxide represented by the following formula (20) and ametal halide represented by the following formula (21):

M⁰(OR)_(t)Y_(u)  (20)

M⁰X_(t)Y_(u)  (21)

[0074] (In the formulas (20) and (21), M⁰ is a positive divalent topentavalent atom, R is an alkyl group or aryl group, Y is a hydrogenatom, alkyl group, aryl group, hydroxyl group, alkoxyl group or aryloxygroup, X is a halogen atom, and t and u are each independently aninteger of 0 or more, with the proviso that (t+u) is equal to thevalence of M⁰.)

[0075] It should be understood that the above hydrolyzate includes whatis obtained by hydrolyzing all the hydrolyzable portions contained in araw material and also what is obtained by hydrolyzing some and not allof the hydrolyzable portions.

[0076] The positive divalent to pentavalent atom M⁰ in the aboveformulas (20) and (21) is, for example, B, Si, P or metal atom. Themetal atom is preferably a group 2A or 3B metal atom of the periodictable or a transition metal atom.

[0077] All the above alkyl groups and alkyl groups contained in theabove alkoxyl groups may be a linear, branched or cyclic alkyl grouphaving 1 to 10 carbon atoms, and some of the hydrogen atoms contained inthe above groups may be substituted by a fluorine atom, or some or allof the hydrogen atoms contained in the above groups may be substitutedby a chlorine atom, bromine atom, perfluoroalkyl group, hydroxyl group,mercapto group, thioalkyl group, alkoxyl group, perfluoroalkoxyl group,alkylester group, alkylthioester group, perfluoroalkylester group, cyanogroup, nitro group or aryl group.

[0078] All the above aryl groups and aryl groups contained in the abovearyloxy groups are each independently a phenyl group, naphthyl group,anthracenyl group, biphenyl group or what is obtained by substituting ahydrogen atom contained in the above groups by a chlorine atom, bromineatom, hydroxyl group, mercapto group, alkoxyl group, thioalkyl group,alkylester group, alkylthioester group, cyano group or nitro group.

[0079] The halogen atom is preferably fluorine, chlorine or bromine.

[0080] Examples of the silicon compound represented by the above formula(20) include tetraalkoxysilanes such as tetramethoxysilane,tetraethoxysilane (generally called TEOS), tetra-n-propyloxysilane,tetraisopropyloxysilane and tetra-n-butoxysilane;monoalkyltrialkoxysilanes such as methyltrimethoxysilane,methyltriethoxysilane, methyltri-n-propyloxysilane, ethyltriethoxysilaneand cyclohexyltriethoxysilane; monoaryltrialkoxysilanes such asphenyltriethoxysilane, naphthyltriethoxysilane,4-chlorophenyltriethoxysilane, 4-cyanophenyltriethoxysilane,4-aminophenyltriethoxysilane, 4-nitrophenyltriethoxysilane,4-methylphenyltriethoxysilane and 4-hydroxyphenyltriethoxysilane;monoaryloxytrialkoxysilanes such as phenoxytriethoxysilane,naphthyloxytriethoxysilane, 4-chlorophenyloxytriethoxysilane,4-cyanophenyltrioxyethoxysilane, 4-aminophenyloxytriethoxysilane,4-nitrophenyloxytriethoxysilane, 4-methylphenyloxytriethoxysilane and4-hydroxyphenyloxytriethoxysilane; monohydroxytrialkoxysilanes such asmonohydroxytrimethoxysilane, monohydroxytriethoxysilane andmonohydroxytri-n-propyloxysilane; dialkyldialkoxysilanes such asdimethyldimethoxysilane, dimethyldiethoxysilane,dimethyldi-n-propyloxysilane, methyl(ethyl)diethoxysilane andmethyl(cyclohexyl)diethoxysilane; monoalkylmonoaryldialkoxysilanes suchas methyl(phenyl)diethoxysilane; diaryldialkoxysilanes such asdiphenyldiethoxysilane; diaryloxydialkoxysilanes such asdiphenoxydiethoxysilane; monoalkylmonoaryloxydialkoxysilanes such asmethyl(phenoxy)diethoxysilane; monoarylmonoaryloxydialkoxysilanes suchas phenyl(phenoxy)diethoxysilane; dihydroxydialkoxysilanes such asdihydroxydimethoxysilane, dihydroxydiethoxysilane anddihydroxydi-n-propyloxysilane: monoalkylmonohydroxydialkoxysilanes suchas methyl(hydroxy)dimethoxysilane; monoarylmonohydroxydialkoxysilanessuch as phenyl(hydroxy)dimethoxysilane; trialkylmonoalkoxysilanes suchas trimethylmethoxysilane, trimethylethoxysilane,trimethyl-n-propyloxysilane, dimethyl(ethyl)ethoxysilane anddimethyl(cyclohexyl)ethoxysilane; dialkylmonoarylmonoalkoxysilanes suchas dimethyl(phenyl)ethoxysilane; monoalkyldiarylmonoalkoxysilanes suchas methyl(diphenyl)ethoxysilane; triaryloxymonoalkoxysilanes such astriphenoxyethoxysilane; monoalkyldiaryloxymonoalkoxysilanes such asmethyl(diphenoxy)ethoxysilane; monoaryldiaryloxymonoalkoxysilanes suchas phenyl(diphenoxy)ethoxysilane; dialkylmonoaryloxymonoalkoxysilanessuch as dimethyl(phenoxy)ethoxysilane;diarylmonoaryloxymonoalkoxysilanes such asdiphenyl(phenoxy)ethoxysilane;monoalkylmonoarylmonoaryloxymonoalkoxysilanes such asmethyl(phenyl)(phenoxy)ethoxysilane; trihydroxymonoalkoxysilanes such astrihydroxymethoxysilane, trihydroxyethoxysilane andtrihydroxy-n-propyloxysilane; and oligomers of the above compounds suchas dimers to pentamers of tetramethoxysilane.

[0081] Examples of the silicon compound represented by the above formula(21) include tetrahalogenosilanes such as tetrachlorosilane,tetrabromosilane, tetraiodosilane, trichlorobromosilane anddichlorodibromosilane; monoalkyltrihalogenosilanes such asmethyltrichlorosilane, methyldichlorobromosilane andcyclohexyltrichlorosilane; monoaryltrihalogenosilanes such asphenyltrichlorosilane, naphthyltrichlorosilane,4-chlorophenyltrichlorosilane and phenyldichlorobromosilane;monoaryloxytrihalogenosilanes such as phenoxytrichlorosilane andphenoxydichlorobromosilane; monoalkoxytrihalogenosilanes such asmethoxytrichlorosilane and ethoxytrichlorosilane;dialkyldihalogenosilanes such as dimethyldichlorosilane,methyl(ethyl)dichlorosilane and methyl(cyclohexyl)dichlorosilane;monoalkylmonoaryldihalogenosilanes such as methyl(phenyl)dichlorosilane;diaryldihalogenosilanes such as diphenyldichlorosilane;diaryloxydihalogenosilanes such as diphenoxydichlorosilane;monoalkylmonoaryloxydihalogenosilanes such asmethyl(phenoxy)dichlorosilane; monoarylmonoaryloxydihalogenosilanes suchas phenyl(phenoxy)dichlorosilane; dialkoxydihalogenosilanes such asdiethoxydichlorosilane; monoalkylmonoalkoxydichlorosilanes such asmethyl(ethoxy)dichlorosilane; monoarylmonoethoxydichlorosilanes such asphenyl(ethoxy)dichlorosilane; trialkylmonohalogenosilanes such astrimethylchlorosilane, dimethyl(ethyl)chlorosilane anddimethyl(cyclohexyl)chlorosilane; dialkylmonoarylmonohalogenosilanessuch as dimethyl(phenyl)chlorosilane; monoalkyldiarylmonohalogenosilanessuch as methyl(diphenyl)chlorosilane; triaryloxymonohalogenosilanes suchas triphenoxychlorosilane; monoalkyldiaryloxymonohalogenosilanes such asmethyl(diphenoxy)chlorosilane; monoaryldiaryloxymonohalogenosilanes suchas phenyl(diphenoxy)chlorosilane; dialkylmonoaryloxymonohalogenosilanessuch as dimethyl(phenoxy)chlorosilane;diarylmonoaryloxymonohalogenosilanes such asdiphenyl(phenoxy)chlorosilane;monoalkylmonoarylmonoaryloxymonohalogenosilanes such asmethyl(phenyl)(phenoxy)chlorosilane; triethoxymonohalogenosilanes suchas triethoxychlorosilane; and oligomers of the above compounds such asdimers to pentamers of tetrachlorosilane.

[0082] Other examples of the compounds represented by the above formula(20) and (21) include alkoxides and halides such as diethoxyberyllium,dichloroberyllium, triethoxyboron, trichloroboron, diethoxymagnesium,dichloromagnesium, triethoxyaluminum, trichloroaluminum,triethoxyphosphorus, trichlorophosphorus, pentaethoxyphosphorus,pentachlorophosphorus, diethoxycalcium, dichlorocalcium,triethoxyscandium, trichloroscandium, tetraethoxytitanium,tetrabutoxytitanium, tetrachlorotitanium, diethoxymanganese,dichloromanganese, diethoxyiron, dichloroiron, triethoxyiron,trichloroiron, diethoxycobalt, dichlorocobalt, diethoxynickel,dichloronickel, diethoxyzinc, dichlorozinc, triethoxygallium,trichlorogallium tetramethoxygermanium, tetraethoxygermanium,tetrachlorogermanium, diethoxystrontium, dichlorostrontium,triethoxyyttrium, trichloroyttrium, tetramethoxyzirconium,tetraethoxyzirconium, tetrachlorozirconium, diethoxycadmium,dichlorocadmium, triethoxyindium, trichloroindium, tetraethoxytellurium,tetrachlorotellurium, diethoxybarium, dichlorobarium,triethoxylanthanum, trichlorolanthanum, triethoxyneodymium,trichloroneodymium, triethoxyytterbium, trichloroytterbium,hexaethoxytungsten, hexachlorotungsten, pentaethoxytantalum,pentachlorotantalum, diethoxylead, dichlorolead, triethoxybismuth,trichlorobismuth, tetraethoxythorium and tetrachlorothorium.

[0083] Out of these, tetraalkoxysilanes such as tetramethoxysilane andtetraethoxysilane; trialkoxyaluminums such as triethoxyaluminum;tetraalkoxytitaniums such as tetraethoxytitaniun; tetrahalogenosilanessuch as tetrachlorosilane; trihalogenoaluminums such astrichloroaluminum; and tetrahalogenotitaniums such astetrachlorotitanium are preferred. More preferred are tetraalkoxysilanessuch as tetramethoxysilane and tetraethoxysilane; trialkoxyaluminumssuch as triethoxyaluminum; and tetrahalogenosilanes such astetrachlorosilane, and the most preferred are tetraalkoxysilanes such astetraethoxysilane. Any number of compounds out of the above compoundsmay be used in combination in any ratio.

[0084] The component (B) used in the present invention can be producedby subjecting the above compound to a hydrolytic reaction. Thehydrolytic reaction is preferably carried out in a suitable solvent.Examples of the solvent include water-soluble solvents such as methanol,ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol,t-butyl alcohol, acetone, tetrahydrofuran, dioxane and acetonitrile andaqueous solutions thereof.

[0085] Since these water-soluble solvents are removed in the subsequentstep, methanol, ethanol, n-propanol, isopropyl alcohol, acetone andtetrahydrofuran having a relatively low boiling point are preferred, andalcohols such as methanol, ethanol, n-propanol and isopropyl alcohol aremore preferred from the view point of solubility for the raw material.The most preferred is ethanol.

[0086] The hydrolytic reaction for synthesizing the component (B) iscarried out in the presence of water and a suitable catalyst asdescribed below.

[0087] Stated more specifically, the compound represented by the aboveformula (20) or (21) is dissolved in a suitable organic solvent andwater is added to this solution intermittently or continuously. Thecatalyst may be dissolved or dispersed in the organic solvent in advanceor dissolved or dispersed in water to be added.

[0088] The temperature for carrying out the hydrolytic reaction isgenerally 0 to 100° C., preferably 15 to 80° C.

[0089] Water for carrying out the hydrolytic reaction is notparticularly limited but preferably ion exchange water.

[0090] The amount of water is 0.25 to 3 mols, particularly preferably0.3 to 2.5 mols based on 1 mol of the total of an alkoxyl group andhalogen atom contained in the compound represented by the above formula(20) or (21).

[0091] The catalyst for carrying out hydrolysis is a metal chelatecompound, organic acid, inorganic acid, organic base or inorganic base.

[0092] Examples of the metal chelate compound used as the catalystinclude titanium chelate compounds such astriethoxy.mono(acetylacetonato)titanium,tri-n-propoxy.mono(acetylacetonato)titanium,tri-i-propoxy.mono(acetylacetonato)titanium,tri-n-butoxy.mono(acetylacetonato)titanium,tri-sec-butoxy.mono(acetylacetonato)titanium,tri-t-butoxy.mono(acetylacetonato)titanium,diethoxy.bis(acetylacetonato)titanium,di-n-propoxy.bis(acetylacetonato)titanium,di-i-propoxy.bis(acetylacetonato)titanium,di-n-butoxy.bis(acetylacetonato)titanium,di-sec-butoxy.bis(acetylacetonato)titanium,di-t-butoxy.bis(acetylacetonato)titanium,monoethoxy.tris(acetylacetonato)titanium,mono-n-propoxy.tris(acetylacetonato)titanium,mono-i-propoxy.tris(acetylacetonato)titanium,mono-n-butoxy.tris(acetylacetonato)titanium,mono-sec-butoxy.tris(acetylacetonato)titanium,mono-t-butoxy.tris(acetylacetonato)titanium,tetrakis(acetylacetonato)titanium,triethoxy.mono(ethylacetoacetate)titanium,tri-n-propoxy.mono(ethylacetoacetate)titanium,tri-i-propoxy.mono(ethylacetoacetate)titanium,tri-n-butoxy.mono(ethylacetoacetate)titanium,tri-sec-butoxy.mono(ethylacetoacetate)titanium,tri-t-butoxy.mono(ethylacetoacetate)titanium,diethoxy.bis(ethylacetoacetate)titanium,di-n-propoxy.bis(ethylacetoacetate)titanium,di-i-propoxy.bis(ethylacetoacetate)titanium,di-n-butoxy.bis(ethylacetoacetate)titanium,di-sec-butoxy.bis(ethylacetoacetate)titanium,di-t-butoxy.bis(ethylacetoacetate)titanium,monoethoxy.tris(ethylacetoacetate)titanium,mono-n-propoxy.tris(ethylacetoacetate)titanium,mono-i-propoxy.tris(ethylacetoacetate)titanium,mono-n-butoxy.tris(ethylacetoacetate)titanium,mono-sec-butoxy.tris(ethylacetoacetate)titanium,mono-t-butoxy.tris(ethylacetoacetate)titanium,tetrakis(ethylacetoacetate)titanium,mono(acetylacetonato)tris(ethylacetoacetate)titanium,bis(acetylacetonato)bis(ethylacetoacetate)titanium andtris(acetylacetonato)mono(ethylacetoacetate)titanium; zirconium chelatecompounds such as triethoxy.mono(acetylacetonato)zirconium,tri-n-propoxy.mono(acetylacetonato)zirconium,tri-i-propoxy.mono(acetylacetonato)zirconium,tri-n-butoxy.mono(acetylacetonato)zirconium,tri-sec-butoxy.mono(acetylacetonato)zirconium,tri-t-butoxy.mono(acetylacetonato)zirconium,diethoxy.bis(acetylacetonato)zirconium,di-n-propoxy.bis(acetylacetonato)zirconium,di-i-propoxy.bis(acetylacetonato)zirconium,di-n-butoxy.bis(acetylacetonato)zirconium,di-sec-butoxy.bis(acetylacetonato)zirconium,di-t-butoxy.bis(acetylacetonato)zirconium,monoethoxy.tris(acetylacetonato)zirconium,mono-n-propoxy.tris(acetylacetonato)zirconium,mono-i-propoxy.tris(acetylacetonato)zirconium,mono-n-butoxy.tris(acetylacetonato)zirconium,mono-sec-butoxy.tris(acetylacetonato)zirconium,mono-t-butoxy.tris(acetylacetonato)zirconium,tetrakis(acetylacetonato)zirconium,triethoxy.mono(ethylacetoacetate)zirconium,tri-n-propoxy.mono(ethylacetoacetate)zirconium,tri-i-propoxy.mono(ethylacetoacetate)zirconium,tri-n-butoxy.mono(ethylacetoacetate)zirconium,tri-sec-butoxy.mono(ethylacetoacetate)zirconium,tri-t-butoxy.mono(ethyiacetoacetate)zirconium,diethoxy.bis(ethylacetoacetate)zirconium,di-n-propoxy.bis(ethylacetoacetate)zirconium,di-i-propoxy.bis(ethylacetoacetate)zirconium,di-n-butoxy.bis(ethylacetoacetate)zirconium,di-sec-butoxy.bis(ethylacetoacetate)zirconium,di-t-butoxy.bis(ethylacetoacetate)zirconium,monoethoxy.tris(ethylacetoacetate)zirconium,mono-n-propoxy.tris(ethylacetoacetate)zirconium,mono-i-propoxy.tris(ethylacetoacetate)zirconium,mono-n-butoxy.tris(ethylacetoacetate)zirconium,mono-sec-butoxy.tris(ethylacetoacetate)zirconium,mono-t-butoxy.tris(ethylacetoacetate)zirconium,tetrakis(ethylacetoacetate)zirconium,mono(acetylacetonato)tris(ethylacetoacetate)zirconium,bis(acetylacetonato)bis(ethylacetoacetate)zirconium andtris(acetylacetonato)mono(ethylacetoacetate)zirconium; and aluminumchelate compounds such as tris(acetylacetonato)aluminum andtris(ethylacetoacetate)aluminum.

[0093] Examples of the organic acid used as the catalyst include aceticacid, propionic acid, butanoic acid, pentanoic acid, hexoic acid,heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalicacid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallicacid, butyric acid, mellitic acid, arachidonic acid, shikimic acid,2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenicacid, salicylic acid, benzoic acid, p-aminobenzoic acid,p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid,dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formicacid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citricacid and tartaric acid.

[0094] Examples of the inorganic acid used as the catalyst includehydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid andphosphoric acid.

[0095] Examples of the organic base used as the catalyst includepyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline,trimethylamine, triethylamine, monoethanolamine, diethanolamine,dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine,diazabicyclooctane, diazabicyclononane, diazabicycloundecene andtetramethylammonium hydroxide.

[0096] Examples of the inorganic base used as the catalyst includeammonia, sodium hydroxide, potassium hydroxide, barium hydroxide andcalcium hydroxide.

[0097] Out of these, a metal chelate compound, an organic acid or aninorganic acid is preferably used as the catalyst and a titanium chelatecompound or an organic acid is more preferably used.

[0098] These compounds may be used alone or in combination of two ormore as the catalyst.

[0099] The amount of the catalyst is preferably 0.001 to 10 parts byweight, more preferably 0.01 to 10 parts by weight based on 100 parts byweight of the compound represented by the above formula (20) or (21) interms of SiO₂.

[0100] Further, it is preferred to remove the residual water and analcohol formed as a reaction by-product after the hydrolysis of thecompound represented by the above formula (20) or (21).

[0101] A ladder type polysilsesquioxane represented by the followingformula (22) may be suitably used as the nondecomposable compound (B):

[0102] wherein R_(X) is a monovalent organic group, R_(Y) is a hydrogenatom or monovalent organic group, R_(X) and R_(Y) may be the same ordifferent, and n is a positive integer corresponding to the molecularweight.

[0103] Examples of the monovalent organic group in the above formula(22) include alkyl group, aryl group, allyl group and glycidyl group.Examples of the alkyl group include methyl group, ethyl group and propylgroup, preferably those having 1 to 5 carbon atoms. These alkyl groupsmay be chain or branched. Examples of the aryl group include phenylgroup, naphthyl group and tolyl group. A hydrogen atom contained in thealkyl group, aryl group, allyl group and glycidyl group may besubstituted by a halogen atom such as chlorine atom or bromine atom,hydroxyl group, mercapto group, alkoxyl group, thioalkyl group,alkylester group, alkylthioester group or aryl group.

[0104] Methods of producing the compound having a structure representedby the above formula (22) are disclosed by JP-A 56-157885, JP-A57-40526, JP-A 58-69217 and the like. Commercially available products ofthe compound include GR-100, GR-650, GR-908 and GR-950 (of Showa DenkoK.K.).

[0105] Not only the compound represented by the above formula (22) butalso a hydrolyzate and condensate thereof may be used as the component(B). The hydrolytic reaction and condensation reaction can be carriedout under conditions (i.e., catalyst, water and reaction temperature)similar to the conditions of the hydrolytic reaction of the compoundsrepresented by the above formulas (20) and (21). The compoundrepresented by the above formula (22) has a weight average molecularweight in terms of polystyrene of preferably 500 to 500,000, morepreferably 500 to 300,000.

[0106] In the present invention, an inorganic oxide particle may be usedtogether with the above resin. The inorganic oxide particle is stable toan acid or base generated from the radiation sensitive decomposer (C)which will be described hereinafter. An oxide particle having apreferred dielectric constant may be selected according to applicationpurpose and used.

[0107] The oxide particle is preferably an oxide containing an atom suchas Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf,Nb, Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Bi or Te, more preferably an oxidesuch as BeO, MgO, CaO, SrO, BaO, Sc₂O₃, Y₂O₃, La₂O₃, Ce₂O₃, Gd₂O₃,Tb₂O₃, Dy₂O₃, Yb₂O₃, Lu₂O₃, TiO₂, ZrO₂, HfO₂, Nb₂O₅, MoO₃, WO₃, ZnO,B₂O₃, Al₂O₃, SiO₂, GeO₂, SnO₂, PbO, Bi₂O₃ or TeO₂, or a composite oxidecontaining any one of these, such as Al₂O₃—MgO, Al₂O₃—SiO₂, ZnO—Y₂O₃,ZrO₂—Ce₂O₃, ZrO₂—TiO₂—SnO₂, TeO₂—BaO—ZnO, TeO₂—WO₃—Ta₂O₅,TeO₂—WO₃—Bi₂O₃, TeO₂—BaO—PbO, CaO—Al₂O₃, CaO—Al₂O₃—BaO, CaO—Al₂O₃—Na₂O,CaO—Al₂O₃—K₂O, CaO—Al₂O₃—SiO₂, PbO—Bi₂O₃—BaO, PbO—Bi₂O₃—ZnO, PbO—Bi₂O₃,PbO—Bi₂O₃—BaO—ZnO, PbO—Bi₂O₃—CdO—Al₂O₃, PbO—Bi₂O₃—GeO₂,PbO—Bi₂O₃—GeO₂—Ti₂O, BaO—PbO—Bi₂O₃, BaO—PbO—Bi₂O₃—ZnO, Bi₂O₃—Ga₂O₃—PbO,Bi₂O₃—Ga₂O₃—CdO or Bi₂O₃—Ga₂O₃—(Pb,Cd)O.

[0108] The particle diameter of the oxide particle is preferably smallerthan the thickness of a film of the dielectric constant changingcomposition of the present invention. It can be, for example, 2 μm orless, preferably 0.2 μm or less, particularly preferably 0.1 μm or less.When the particle diameter is larger than 2 μm, the obtained film of thedielectric constant changing composition may have a problem with itssurface condition.

[0109] The surface of the above oxide particle may be modified bycontacting a silane coupling agent, surfactant or coordinating compoundhaving coordinating ability to a metal atom constituting the oxidebefore use.

[0110] The inorganic oxide particle is used in an amount of preferably500 parts or less by weight, more preferably 300 parts or less by weightbased on 100 parts by weight of the hydrolyzate.

[0111] The weight average molecular weight of the nondecomposablecompound (B) is preferably 200 to 1,000,000, more preferably 200 to500,000.

[0112] The amount of the component (B) is preferably 5 to 90 parts byweight, more preferably 10 to 70 parts by weight based on 100 parts byweight of the total of the component (B) and the component (A). When theamount of the component (B) is smaller than 5 parts by weight, thedielectric constant changing material becomes brittle and when theamount of the component (B) is larger than 90 parts by weight, theobtained dielectric constant difference is apt to be small.

[0113] It is a matter of course that the component (B) and the component(A) can be produced separately. The component (A) may be produced in thepresence of the component (B) prepared in advance, the component (B) maybe produced in the presence of the component (A) prepared in advance, orthe components (A) and (B) may be produced in the same reaction systembefore use.

[0114] (C) Radiation Sensitive Decomposer

[0115] The radiation sensitive decomposer (C) used in the presentinvention can be a radiation sensitive acid generator or a radiationsensitive base generator. Preferably, when an acid decomposable compoundis used as the decomposable compound (A), a radiation sensitive acidgenerator is used as the radiation sensitive decomposer (C) and when abase decomposable compound is used as the decomposable compound (A), aradiation sensitive base generator is used as the radiation sensitivedecomposer (C).

[0116] The above radiation sensitive acid generator is selected from atrichloromethyl-s-triazine, diaryl iodonium salt, triaryl sulfoniumsalt, quaternary ammonium salt and sulfonic acid ester.

[0117] Examples of the trichloromethyl-s-triazine includetris(2,4,6-trichloromethyl)-s-triazine,2-phenyl-bis(4,6-trichloromethyl)-s-triazine,2-(4-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(2-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(2-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(2-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine,2-(2-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methoxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-methoxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-(2-methoxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-(3,4,5-trimethoxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methylthio-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-methylthio-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-(3-methylthio-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-piperonyl-bis(4,6-trichloromethyl)-s-triazine,2-[2-(furan-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine,2-[2-(5-methylfuran-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazineand2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine.

[0118] Examples of the above diaryl iodonium salt includediphenyliodonium tetrafluoroborate, diphenyliodoniumhexafluorophosphonate, diphenyliodonium hexafluoroarsenate,diphenyliodonium trifluoromethane sulfonate, diphenyliodoniumtrifluoroacetate, diphenyliodonium-p-toluene sulfonate, diphenyliodoniumbutyltris(2,6-difluorophenyl)borate, diphenyliodoniumhexyltris(p-chlorophenyl)borate, diphenyliodoniumhexyltris(3-trifluoromethylphenyl)borate, 4-methoxyphenylphenyliodoniumtetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate,4-methoxyphenylphenyliodonium hexafluoroarsenate,4-methoxyphenylphenyliodonium trifluoromethane sulfonate,4-methoxyphenylphenyliodonium trifluoroacetate,4-methoxyphenylphenyliodonium-p-toluene sulfonate,4-methoxyphenylphenyliodonium butyltris(2,6-difluorophenyl)borate,4-methoxyphenylphenyliodonium hexyltris(p-chlorophenyl)borate,4-methoxyphenylphenyliodonium hexyltris(3-trifluoromethylphenyl)borate,bis(4-tert-butylphenyl)iodonium tetrafluoroborate,bis(4-tert-butylphenyl)iodonium hexafluoroarsenate,bis(4-tert-butylphenyl)iodonium trifluoromethane sulfonate,bis(4-tert-butylphenyl)iodonium trifluoroacetate,bis(4-tert-butylphenyl)iodonium-p-toluene sulfonate,bis(4-tert-butylphenyl)iodonium butyltris(2,6-difluorophenyl)borate,bis(4-tert-butylphenyl)iodonium hexyltris(p-chlorophenyl)borate andbis(4-tert-butylphenyl)iodoniumhexyltris(3-trifluoromethylphenyl)borate.

[0119] Examples of the above triaryl sulfonium salt includetriphenylsulfonium tetrafluoroborate, triphenylsulfoniumhexafluorophosphonate, triphenylsulfonium hexafluoroarsenate,triphenylsulfonium trifluoromethane sulfonate, triphenylsulfoniumtrifluoroacetate, triphenylsulfonium-p-toluene sulfonate,triphenylsulfonium butyltris(2,6-difluorophenyl)borate,triphenylsulfonium hexyltris(p-chlorophenyl)borate, triphenylsulfoniumhexyltris(3-trifluoromethylphenyl)borate,4-methoxyphenyldiphenylsulfonium tetrafluoroborate,4-methoxyphenyldiphenylsulfonium hexafluorophosphonate,4-methoxyphenyldiphenylsulfonium hexafluoroarsenate,4-methoxyphenyldiphenylsulfonium trifluoromethane sulfonate,4-methoxyphenyldiphenylsulfonium trifluoroacetate,4-methoxyphenyldiphenylsulfonium-p-toluene sulfonate,4-methoxyphenyldiphenylsulfonium butyltris(2,6-difluorophenyl)borate,4-methoxyphenyldiphenylsulfonium hexyltris(p-chlorophenyl)borate,4-methoxyphenyldiphenylsulfoniumhexyltris(3-trifluoromethylphenyl)borate,4-phenylthiophenyldiphenylsulfonium tetrafluoroborate,4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate,4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate,4-phenylthiophenyldiphenylsulfonium trifluoromethane sulfonate,4-phenylthiophenyldiphenylsulfonium trifluoroacetate,4-phenylthiophenyldiphenylsulfonium-p-toluene sulfonate,4-phenylthiophenyldiphenylsulfonium butyltris(2,6-difluorophenyl)borate,4-phenylthiophenyldiphenylsulfonium hexyltris(p-chlorophenyl)borate,4-phenylthiophenyldiphenylsulfoniumhexyltris(3-trifluoromethylphenyl)borate,4-hydroxy-1-naphthalenyldimethylsulfonium tetrafluoroborate,4-hydroxy-1-naphthalenyldimethylsulfonium hexafluorophosphonate,4-hydroxy-1-naphthalenyldimethylsulfonium hexafluoroarsenate,4-hydroxy-1-naphthalenyldimethylsulfonium trifluoromethane sulfonate,4-hydroxy-1-naphthalenyldimethylsulfonium trifluoroacetate,4-hydroxy-1-naphthalenyldimethylsulfonium-p-toluene sulfonate,4-hydroxy-1-naphthalenyldimethylsulfoniumbutyltris(2,6-difluorophenyl)borate,4-hydroxy-1-naphthalenyldimethylsulfoniumhexyltris(p-chlorophenyl)borate and4-hydroxy-1-naphthalenyldimethylsulfoniumhexyltris(3-trifluoromethylphenyl)borate.

[0120] Examples of the above quaternary ammonium salt includetetramethylammonium tetrafluoroborate, tetramethylammoniumhexafluorophosphonate, tetramethylammonium hexafluoroarsenate,tetramethylammonium trifluoromethane sulfonate, tetramethylammoniumtrifluoroacetate, tetramethylammonium-p-toluene sulfonate,tetramethylammonium butyltris(2,6-difluorophenyl)borate,tetramethylammonium hexyltris(p-chlorophenyl)borate, tetramethylammoniumhexyltris(3-trifluoromethylphenyl)borate, tetrabutylammoniumtetrafluoroborate, tetrabutylammonium hexafluorophosphonate,tetrabutylammonium hexafluoroarsenate, tetrabutylammoniumtrifluoromethane sulfonate, tetrabutylammonium trifluoroacetate,tetrabutylammonium-p-toluene sulfonate, tetrabutylammoniumbutyltris(2,6-difluorophenyl)borate, tetrabutylammoniumhexyltris(p-chlorophenyl)borate, tetrabutylammoniumhexyltris(3-trifluoromethylphenyl)borate, benzyltrimethylammoniumtetrafluoroborate, benzyltrimethylammonium hexafluorophosphonate,benzyltrimethylammonium hexafluoroarsenate, benzyltrimethylammoniumtrifluoromethane sulfonate, benzyltrimethylammonium trifluoroacetate,benzyltrimethylammonium-p-toluene sulfonate, benzyltrimethylammoniumbutyltris(2,6-difluorophenyl)borate, benzyltrimethylammoniumhexyltris(p-chlorophenyl)borate, benzyltrimethylammoniumhexyltris(3-trifluoromethylphenyl)borate, benzyldimethylphenylammoniumtetrafluoroborate, benzyldimethylphenylammonium hexafluorophosphonate,benzyldimethylphenylammonium hexafluoroarsenate,benzyldimethylphenylammonium trifluoromethane sulfonate,benzyldimethylphenylammonium trifluoroacetate,benzyldimethylphenylammonium-p-toluene sulfonate,benzyldimethylphenylammonium butyltris(2,6-difluorophenyl)borate,benzyldimethylphenylammonium hexyltris(p-chlorophenyl)borate,benzyldimethylphenylammonium hexyltris(3-trifluoromethylphenyl)borate,N-cinnamylideneethylphenylammonium tetrafluoroborate,N-cinnamylideneethylphenylammonium hexafluorophosphonate,N-cinnamylideneethylphenylammonium hexafluoroarsenate,N-cinnamylideneethylphenylammonium trifluoromethane sulfonate,N-cinnamylideneethylphenylammonium trifluoroacetate,N-cinnamylideneethylphenylammonium-p-toluene sulfonate,N-cinnamylideneethylphenylammonium butyltris(2,6-difluorophenyl)borate,N-cinnamylideneethylphenylammonium hexyltris(p-chlorophenyl)borate andN-cinnamylideneethylphenylammoniumhexyltris(3-trifluoromethylphenyl)borate.

[0121] Examples of the above sulfonic acid ester includeα-hydroxymethylbenzoin-p-toluenesulfonic acid ester,α-hydroxymethylbenzoin-trifluoromethanesulfonic acid ester,α-hydroxymethylbenzoin-methanesulfonic acid ester,pyrogallol-tri(p-toluenesulfonic acid) ester,pyrogallol-tri(trifluoromethanesulfonic acid)ester,pyrogallol-trimethanesulfonic acid ester,2,4-dinitrobenzyl-p-toluenesulfonic acid ester,2,4-dinitrobenzyl-trifluoromethanesulfonic acid ester,2,4-dinitrobenzyl-methanesulfonic acid ester,2,4-dinitrobenzyl-1,2-naphthoquinonediazido-5-sulfonic acid ester,2,6-dinitrobenzyl-p-toluenesulfonic acid ester,2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester,2,6-dinitrobenzyl-methanesulfonic acid ester,2,6-dinitrobenzyl-1,2-naphthoquinonediazido-5-sulfonic acid ester,2-nitrobenzyl-p-toluenesulfonic acid ester,2-nitrobenzyl-trifluoromethanesulfonic acid ester,2-nitrobenzyl-methanesulfonic acid ester,2-nitrobenzyl-1,2-naphthoquinonediazido-5-sulfonic acid ester,4-nitrobenzyl-p-toluenesulfonic acid ester,4-nitrobenzyl-trifluoromethanesulfonic acid ester,4-nitrobenzyl-methanesulfonic acid ester,4-nitrobenzyl-1,2-naphthoquinonediazido-5-sulfonic acid ester,N-hydroxynaphthalimido-p-toluenesulfonic acid ester,N-hydroxynaphthalimido-trifluoromethanesulfonic acid ester,N-hydroxynaphthalimido-methanesulfonic acid ester,N-hydroxy-5-norbornene-2,3-dicarboxyimido-p-toluenesulfonic acid ester,N-hydroxy-5-norbornene-2,3-dicarboxyimido-trifluoromethanesulfonic acidester, N-hydroxy-5-norbornene-2,3-dicarboxyimido-methanesulfonic acidester,2,4,6,3′,4′,5′-hexahydroxybenzophenone-1,2-naphthoquinonediazido-4-sulfonicacid ester and1,1,1-tri(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazido-4-sulfonicacid ester.

[0122] Out of these compounds,2-(3-chlorophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methoxyphenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methylthiophenyl)-bis(4,6-trichloromethyl)-s-triazine,2-(4-methoxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazine,2-piperonyl-bis(4,6-trichloromethyl)-s-triazine,2-[2-(furan-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine,2-[2-(5-methylfuran-2-yl)ethenyl]-bis(4,6-trichloromethyl)-s-triazine,2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-bis(4,6-trichloromethyl)-s-triazineand 2-(4-methoxynaphthyl)-bis(4,6-trichloromethyl)-s-triazine arepreferred as trichloromethyl-s-triazines; diphenyliodoniumtrifluoroacetate, diphenyliodonium trifluoromethane sulfonate,4-methoxyphenylphenyliodonium trifluoromethane sulfonate and4-methoxyphenylphenyliodonium trifluoroacetate are preferred as diaryliodonium salts; triphenylsulfonium trifluoromethane sulfonate,triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfoniumtrifluoromethane sulfonate, 4-methoxyphenyldiphenylsulfoniumtrifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate and 4-phenylthiophenyldiphenylsulfonium trifluoroacetate arepreferred as triaryl sulfonium salts; tetramethylammoniumbutyltris(2,6-difluorophenyl)borate, tetramethylammoniumhexyltris(p-chlorophenyl)borate, tetramethylammoniumhexyltris(3-trifluoromethylphenyl)borate, benzyldimethylphenylammoniumbutyltris(2,6-difluorophenyl)borate, benzyldimethylphenylammoniumhexyltris(p-chlorophenyl)borate and benzyldimethylphenylammoniumhexyltris(3-trifluoromethylphenyl)borate are preferred as quaternaryammonium salts; and 2,6-dinitrobenzyl-p-toluenesulfonic acid ester,2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester,N-hydroxynaphthalimido-p-toluenesulfonic acid ester andN-hydroxynaphthalimido-trifluoromethanesulfonic acid ester are preferredas sulfonic acid esters.

[0123] What are disclosed by JP-A 4-330444; “Polymer”, pp. 242-248, vol.46, No. 6 (1997) and U.S. Pat. No. 5,627,010 are advantageously used asthe above radiation sensitive base generator. However, the radiationsensitive base generator is not limited to these if it generates a baseupon exposure to radiation.

[0124] The preferred radiation sensitive base generator in the presentinvention is selected from a photo active carbamate such as triphenylmethanol, benzyl carbamate or benzoin carbamate; amide such aso-carbamoyl hydroxylamide, o-carbamoyloxime, aromatic sulfonamide,alpha-lactam or N-(2-allylethynyl)amide, and other amide; and oximeester, α-aminoacetophenone and cobalt complex.

[0125] Illustrative examples of the radiation sensitive base generatorinclude compounds represented by the following formulas (23) to (33):

[0126] wherein R⁷² is an alkyl group having 1 to 6 carbon atoms, alkoxylgroup having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbonatoms, dialkylamino group having 1 to 6 carbon atoms for each alkylgroup, piperidyl group, nitro group, hydroxy group, mercapto group,alkenyl group or alkynyl group having 2 to 6 carbon atoms, aryl grouphaving 6 to 20 carbon atoms, fluorine atom, chlorine atom or bromineatom, k is an integer of 0 to 3, R⁷³ is a hydrogen atom, alkyl grouphaving 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6carbon atoms, or aryl group having 6 to 20 carbon atoms, and R⁷⁴ and R⁷⁵are each independently a hydrogen atom, alkyl group having 1 to 6 carbonatoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, arylgroup having 6 to 20 carbon atoms or benzyl group, or R⁷⁴ and R⁷⁵ may bebonded together to form a cyclic structure having 5 to 6 carbon atomstogether with a nitrogen atom bonded thereto,

[0127] wherein R⁷⁶ is an alkyl group having 1 to 6 carbon atoms, alkoxylgroup having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbonatoms, dialkylamino group having 1 to 6 carbon atoms for each alkylgroup, piperidyl group, nitro group, hydroxy group, mercapto group,alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl grouphaving 6 to 20 carbon atoms, R⁷⁷ is a hydrogen atom, alkyl group having1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbonatoms, or aryl group having 6 to 20 carbon atoms, and R⁷⁸ and R⁷⁹ areeach independently a hydrogen atom, alkyl group having 1 to 6 carbonatoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, arylgroup having 6 to 20 carbon atoms or benzyl group, or R⁷⁸ and R⁷⁹ may bebonded together to form a cyclic structure having 5 to 6 carbon atoms,

[0128] wherein R⁸⁰ is an alkyl group having 1 to 6 carbon atoms, alkenylgroup or alkynyl group having 2 to 6 carbon atoms, or aryl group having6 to 20 carbon atoms, and R⁸¹ and R⁸² are each independently a hydrogenatom, alkyl group having 1 to 6 carbon atoms, alkenyl group or alkynylgroup having 2 to 6 carbon atoms, aryl group having 6 to 20 carbon atomsor benzyl group, or R⁸¹ and R⁸² may be bonded together to form a cyclicstructure having 5 to 6 carbon atoms,

[0129] wherein R⁸³ and R⁸⁴ are each independently an alkyl group having1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbonatoms, or aryl group having 6 to 20 carbon atoms,

[0130] wherein R⁸⁵, R⁸⁶ and R⁸⁷ are each independently an alkyl grouphaving 1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6carbon atoms, or aryl group having 6 to 20 carbon atoms,

[0131] wherein R⁸⁸ is an alkyl group having 1 to 6 carbon atoms, alkoxylgroup having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbonatoms, dialkylamino group having 1 to 6 carbon atoms for each alkylgroup, piperidyl group, nitro group, hydroxy group, mercapto group,alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl grouphaving 6 to 20 carbon atoms, R⁸⁹ is a hydrogen atom, alkyl group having1 to 6 carbon atoms, alkenyl group or alkynyl group having 2 to 6 carbonatoms, or aryl group having 6 to 20 carbon atoms, and R⁹⁰, R⁹¹ and R⁹²are each independently a hydrogen atom, alkyl group having 1 to 6 carbonatoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, arylgroup having 6 to 20 carbon atoms or benzyl group,

[0132] wherein R⁹³ is an alkyl group having 1 to 6 carbon atoms, alkoxylgroup having 1 to 6 carbon atoms, thioalkyl group having 1 to 6 carbonatoms, dialkylamino group having 1 to 6 carbon atoms for each alkylgroup, piperidyl group, nitro group, hydroxy group, mercapto group,alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl grouphaving 6 to 20 carbon atoms, R⁹⁴ and R⁹⁵ are each independently ahydrogen atom, hydroxyl group, mercapto group, cyano group, phenoxygroup, alkyl group having 1 to 6 carbon atoms, fluorine atom, chlorineatom, bromine atom, alkenyl group or alkynyl group having 2 to 6 carbonatoms, or aryl group having 6 to 20 carbon atoms, and R⁹⁶ and R⁹⁷ areeach independently a hydrogen atom, alkyl group having 1 to 6 carbonatoms, alkenyl group or alkynyl group having 2 to 6 carbon atoms, arylgroup having 6 to 20 carbon atoms or benzyl group, or R⁹⁶ and R⁹⁷ may bebonded together to form a cyclic structure having 5 to 6 carbon atoms,

[0133] wherein R⁹⁸ and R⁹⁹ are each independently an alkyl group having1 to 6 carbon atoms, alkoxyl group having 1 to 6 carbon atoms, thioalkylgroup having 1 to 6 carbon atoms, dialkylamino group having 1 to 6carbon atoms for each alkyl group, piperidyl group, nitro group, hydroxygroup, mercapto group, alkenyl group or alkynyl group having 2 to 6carbon atoms, or aryl group having 6 to 20 carbon atoms, R¹⁰⁰ to R¹⁰³are each independently a hydrogen atom, hydroxyl group, mercapto group,cyano group, phenoxy group, alkyl group having 1 to 6 carbon atoms,fluorine atom, chlorine atom, bromine atom, alkenyl group or alkynylgroup having 2 to 6 carbon atoms, or aryl group having 6 to 20 carbonatoms, and A⁵ is a divalent atomic group formed by excluding twohydrogen atoms bonded to one or two nitrogen atoms of amonoalkylamine,piperazine, aromatic diamine or aliphatic diamine,

[0134] wherein R¹⁰⁴ and R¹⁰⁵ are each independently an alkyl grouphaving 1 to 6 carbon atoms, alkoxyl group having 1 to 6 carbon atoms,thioalkyl group having 1 to 6 carbon atoms, dialkylamino group having 1to 6 carbon atoms for each alkyl group, piperidyl group, nitro group,hydroxy group, mercapto group, alkenyl group or alkynyl group having 2to 6 carbon atoms, or aryl group having 6 to 20 carbon atoms, R¹⁰⁶ andR¹⁰⁷ are each independently a hydrogen atom, hydroxyl group, mercaptogroup, cyano group, phenoxy group, alkyl group having 1 to 6 carbonatoms, fluorine atom, chlorine atom, bromine atom, alkenyl group oralkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to 20carbon atoms, R¹⁰⁸ to R¹¹¹ are each independently a hydrogen atom, alkylgroup having 1 to 6 carbon atoms, alkenyl group or alkynyl group having2 to 6 carbon atoms, aryl group having 6 to 20 carbon atoms or benzylgroup, or R¹⁰⁸ and R¹⁰⁹, and R¹¹⁰ and R¹¹¹ may be bonded together toform a cyclic structure having 5 to 6 carbon atoms, and A⁶ is analkylene group having 1 to 6 carbon atoms, cyclohexylene group,phenylene group or single bond,

[0135] wherein R¹¹² to R¹¹⁴ are each independently a hydrogen atom,fluorine atom, chlorine atom, bromine atom, alkyl group having 1 to 6carbon atoms, alkenyl group having 1 to 6 carbon atoms, alkynyl grouphaving 1 to 6 carbon atoms, alkoxyl group having 1 to 6 carbon atoms,alkenyl group or alkynyl group having 2 to 6 carbon atoms, or aryl grouphaving 6 to 20 carbon atoms,

L_(n)CO³⁺.3[(R¹¹⁵)₃R¹¹⁶]⁻  (33)

[0136] wherein L is at least one ligand selected from the groupconsisting of ammonia, pyridine, imidazole, ethylenediamine,trimethylenediamine, tetramethylenediamine, hexamethylenediamine,propylenediamine, 1,2-cyclohexanediamine, N,N-diethylethylenediamine anddiethylenetriamine, n is an integer of 2 to 6, R¹¹⁵ is an alkenyl groupor alkynyl group having 2 to 6 carbon atoms, or aryl group having 6 to20 carbon atoms, and R¹¹⁶ is an alkyl group having 1 to 18 carbon atoms.

[0137] In all the above formulas (23) to (33), the alkyl group may belinear, branched or cyclic. Examples of the alkenyl group include vinylgroup and propylenyl group, examples of the alkynyl group includeacetylenyl group, and examples of the aryl group include phenyl group,naphthyl group and anthracenyl group. What contain a fluorine atom,chlorine atom, bromine atom, haloalkyl group, hydroxyl group, carboxylgroup, mercapto group, cyano group, nitro group, azido group,dialkylamino group, alkoxyl group or thioalkyl group substituted for thehydrogen atoms of the above groups are also included.

[0138] Out of these radiation sensitive base generators, preferred are2-nitrobenzylcyclohexyl carbamate, triphenyl methanol,o-carbamoylhydroxylamide, o-carbamoyloxime,[[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine,bis[[(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine,4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane,(4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane,N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III)tris(triphenylmethylborate) and2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone.

[0139] The above radiation sensitive decomposer (C) is used in an amountof preferably 0.01 part or more by weight, more preferably 0.05 part ormore by weight based on 100 parts by weight of the total of thedecomposable compound (A) and the nondecomposable component (B)containing an inorganic oxide particle. When the amount of the component(C) is smaller than 0.01 part by weight, sensitivity to radiation maybecome insufficient. The upper limit value is preferably 30 parts byweight, more preferably 20 parts by weight.

[0140] (D) Stabilizer

[0141] The stabilizer (D) used in the present invention has the functionof stabilizing the residual decomposable compound (A) contained in thedielectric constant changing composition after exposure to radiation toprovide stability to an acid or base. This stabilization prevents achange in dielectric constant and hence the deterioration of adielectric constant pattern formed by the method of the presentinvention even when it is used under the condition that light having awavelength close to the wavelength used to change the dielectricconstant passes therethrough.

[0142] The above stabilizer (D) is selected from an amino compound,epoxy compound, thiirane compound, oxetane compound, alkoxymethylmelamine compound, alkoxymethyl glycoluril compound, alkoxymethylbenzoguanamine compound, alkoxymethyl urea compound, isocyanatecompound, cyanate compound, oxazoline compound, oxazine compound andsilyl compound (halogenated silyl compound and other silyl compound).

[0143] Examples of the above amino compound include ammonia,trimethylamine, triethylamine, tripropylamine, tributylamine,tripentylamine, trihexylamine, tricyclohexylamine, triphenylamine,tribenzylamine, aniline, ethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, 1,3-diaminopropane,1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane,1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane,1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane,1,4-diaminocyclohexane, 1,3-cyclohexanebis(methylamine),1,3-propane-2-ol, 2,2′,2″-triaminotriethylamine,1,4-diamino-2,2,3,3-tetrafluoropentane,1,5-diamino-2,2,3,3,4,4-hexafluoropentane, melamine, benzoguanamine,acetoguanamine, acryloguanamine, paramine, amidol, m-phenylenediamine,p-phenylenediamine, p,p′-diaminodiphenylmethane, diaminodiphenylsulfone,1,8-diaminonaphthalene, 3,5-diamino-1,2,4-triazole,2-chloro-4,6-diamino-s-triazine, 2,6-diaminopyridine,3,3′-diaminobenzidine, bis(4-aminophenyl)ether, m-xylylenediamine,p-xylylenediamine, 1,2,4,5-benzenetetramine, 2,4-diamino-1,3,5-triazine,4,4′-diaminobenzophenone, 3,3′,4,4′-tetraaminobenzophenone,triaminobenzene, 4,4′-thiodianiline,2,3,5,6-tetrabromo-p-xylylenediamine,2,3,5,6-tetrachloro-p-xylylenediamine,4,5-methylenedioxy-1,2-phenylenediamine and2,2′-bis(5-aminopyridyl)sulfide.

[0144] Examples of the above epoxy compound include bisphenol A epoxyresin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresolnovolak epoxy resin, cyclic aliphatic epoxy resin, bisphenol A epoxycompound and aliphatic polyglycidyl ether.

[0145] Examples of commercially available products of the abovecompounds are given below. Commercially available products of thebisphenol A epoxy resin include Epicoat 1001, 1002, 1003, 1004, 1007,1009, 1010 and 828 (of Yuka Shell Epoxy Co., Ltd.), those of thebisphenol F epoxy resin include Epicoat 807 (of Yuka Shell Epoxy Co.,Ltd.), those of the phenol novolak epoxy resin include Epicoat 152 and154 (of Yuka Shell Epoxy Co., Ltd.) and EPPN201 and 202 (of NipponKayaku Co., Ltd.), those of the cresol novolak epoxy resin includeEOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (ofNippon Kayaku Co., Ltd.) and Epicoat 180S75 (of Yuka Shell Epoxy Co.,Ltd.), those of the cyclic aliphatic epoxy resin include CY175, CY177and CY179 (of CIBA-GEIGY A.G.), ERL-4234, ERL-4299, ERL-4221 andERL-4206 (of U.C.C. Co., Ltd.), Showdyne 509 (of Showa Denko K.K.),Araldyte CY-182, CY-192 and CY-184 (of CIBA-GEIGY A.G.), Epichlon 200and 400 (of Dainippon Ink and Chemicals, Inc.), Epicoat 871 and 872 (ofYuka Shell Epoxy Co., Ltd.) and ED-5661 and ED-5662 (of Celanees CoatingCo., Ltd.), and those of the aliphatic polyglycidyl ether includeEpolite 100MF (of Kyoeisha Kagaku Co., Ltd.) and Epiol TMP (of NOFCorporation).

[0146] Besides the above compounds, phenylglycidyl ether, butylglycidylether, 3,3,3-trifluoromethylpropylene oxide, styrene oxide,hexafluoropropylene oxide, cyclohexene oxide, N-glycidylphthalimide,(nonafluoro-N-butyl)epoxide, perfluoroethylglycidyl ether,epichlorohydrin, epibromohydrin, N,N-diglycidylaniline and3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane can be advantageously usedas an epoxy compound.

[0147] Examples of the above thiirane compound include what are obtainedby substituting the epoxy groups of the above epoxy compounds with anethylene sulfide group as shown in J. Org. Chem., 28, 229 (1963), forexample.

[0148] Examples of the above oxetane compound includebis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene (trade name of XDO,manufactured by Toagosei Chemical Industry Co., Ltd.),.bis[(3-ethyl-3-oxetanylmethoxy)methyl-phenyl]methane,bis[(3-ethyl-3-oxetanylmethoxy)methyl-phenyl]ether,bis[(3-ethyl-3-oxetanylmethoxy)methyl-phenyl]propane,bis[(3-ethyl-3-oxetanylmethoxy)methyl-phenyl]sulfone,bis[(3-ethyl-3-oxetanylmethoxy)methyl-phenyl]ketone,bis[(3-ethyl-3-oxetanylmethoxy)methyl-phenyl]hexafluoro propane,tri[(3-ethyl-3-oxetanylmethoxy)methyl]benzene andtetra[(3-ethyl-3-oxetanylmethoxy)methyl]benzene.

[0149] The above alkoxymethyl melamine compound, alkoxymethylbenzoguanamine compound, alkoxymethyl glycoluril compound andalkoxymethyl urea compound are obtained by substituting the methylolgroups of a methylol melamine compound, methylol benzoguanaminecompound, methylol glycoluril compound and methylol urea compound withan alkoxymethyl group, respectively. The type of the alkoxymethyl groupis not particularly limited, as exemplified by methoxymethyl group,ethoxymethyl group, propoxymethyl group and butoxymethyl group.

[0150] Commercially available products of the above compounds includeSimel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202,1156, 1158, 1123, 1170 and 1174, and UFR65 and 300 (of Mitsui SianamidCo., Ltd.), and Nicalak Mx-750, Mx-032, Mx-706, Mx-708, Mx-40, Mx-31,Ms-11 and Mw-30 (of Sanwa Chemical Co., Ltd.).

[0151] Examples of the above isocyanate compound includephenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate,1-methoxyphenylene-2,4-diisocyanate, 1-methylphenylene-2,4-diisocyanate,2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylenediisocyanate, 1,4-xylylene diisocyanate, biphenylene-4,4′-diisocyanate,3,3′-dimethoxybiphenylene-4,4′-diisocyanate,3,3′-dimethylbiphenylene-4,4′-diisocyanate,diphenylmethane-2,4′-diisocyanate, diphenylmethane-4,4′-diisocyanate,3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate,3,3′-dimethyldiphenylmethane-4,4′-diisocyanate,naphthylene-1,5-diisocyanate, cyclobutylene-1,3-diisocyanate,cyclopentylene-1,3-diisocyanate, cyclohexylene-1,3-diisocyanate,cyclohexylene-1,4-diisocyanate, 1-methylcyclohexylene-2,4-diisocyanate,1-methylcyclohexylene-2,6-diisocyanate,1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane,cyclohexane-1,3-bis(methylisocyanate),cyclohexane-1,4-bis(methylisocyanate), isophorone diisocyanate,dicyclohexylmethane-2,4′-diisocyanate,dicyclohexylmethane-4,4′-diisocyanate, ethylene diisocyanate,tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate,dodecamethylene-1,12-diisocyanate, lysine diisocyanate methyl ester andprepolymers having an isocyanate group at both terminals obtained from areaction between a stoichiometrically excessive amount of one of theabove organic diisocyanates and a bifunctional activehydrogen-containing compound.

[0152] The above diisocyanate may be used in combination with an organicpolyisocyanate having 3 or more isocyanate groups, such asphenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4′-triisocyanate,diphenylmethane-2,5,4′-triisocyanate,triphenylmethane-2,4′,4″-triisocyanate,triphenylmethane-4,4′,4″-triisocyanate,diphenylmethane-2,4,2′,4′-tetraisocyanate,diphenylmethane-2,5,2′,5′-tetraisocyanate,cyclohexane-1,3,5-triisocyanate,cyclohexane-1,3,5-tris(methylisocyanate),3,5-dimethylcyclohexane-1,3,5-tris(methylisocyanate),1,3,5-trimethylcyclohexane-1,3,5-tris(methylisocyanate),dicyclohexylmethane-2,4,2′-triisocyanate,dicyclohexylmethane-2,4,4′-triisocyanate or a prepolymer having anisocyanate group at a terminal obtained from a reaction between astoichiometrically excessive amount of one of the above organicpolyisocyanates having 3 or more isocyanate groups and a polyfunctionalactive hydrogen-containing compound having 2 or more hydrogen atoms.

[0153] Examples of the above cyanate compound include1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene,1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene,1,3,6-tricyanatonaphthalene, 2,2′- or 4,4′-dicyanatobiphenyl,bis(4-cyanatophenyl)methane, 2,2-bis(4-cyanatophenyl)propane,2,2′-bis(3,5-dichloro-4-cyanatophenyl)propane,2,2-bis(4-cyanatophenyl)ethane, bis(4-cyanatophenyl)ether,bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone,1,1,1,3,3,3-hexafluoro-2,2-bis(4-cyanatophenyl)propane,tris(4-cyanatophenyl)phosphite, tris(4-cyanatophenyl)phosphate andbenzene polynuclear polyisocyanate compounds obtained from a reactionbetween a phenolic resin and halogenated cyan (for example, JP-B45-11712 and JP-B 55-9433) (the term “JP-B” as used herein means an“examined Japanese patent publication”). A divalent cyanic acid estercompound derived from a bisphenol such as2,2-bis(4-cyanatophenyl)propane is particularly preferred because it iseasily acquired and provides excellent moldability and favorableproperties to the final cured product. A polycyanato obtained byreacting an initial condensate of a phenol and formaldehyde withhalogenated cyan is also useful.

[0154] Examples of the above oxazoline compound include2,2′-bis(2-oxazoline), 4-furan-2-ylmethylene-2-phenyl-4H-oxazol-5-one,1,4-bis(4,5-dihydro-2-oxazolyl)benzene,1,3-bis(4,5-dihydro-2-oxazolyl)benzene,2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane,2,2′-bis-4-benzyl-2-oxazoline,2,6-bis(isopropyl-2-oxazolin-2-yl)pyridine,2,2′-isopropylidenebis(4-tert-butyl-2-oxazoline),2,2′-isopropylidenebis(4-phenyl-2-oxazoline),2,2′-methylenebis(4-tert-butyl-2-oxazoline) and2,2′-methylenebis(4-phenyl-2-oxazoline).

[0155] Examples of the above oxazine compound include2,2′-bis(2-oxazine), 4-furan-2-ylmethylene-2-phenyl-4H-oxazyl-5-one,1,4-bis(4,5-dihydro-2-oxazyl)benzene,1,3-bis(4,5-dihydro-2-oxazyl)benzene,2,3-bis(4-isopropenyl-2-oxazine-2-yl)butane,2,2′-bis-4-benzyl-2-oxazine, 2,6-bis(isopropyl-2-oxazine-2-yl)pyridine,2,2′-isopropylidenebis(4-tert-butyl-2-oxazine),2,2′-isopropylidenebis(4-phenyl-2-oxazine),2,2′-methylenebis(4-tert-butyl-2-oxazine) and2,2′-methylenebis(4-phenyl-2-oxazine).

[0156] Examples of the above halogenated silyl compound includetetrahalogenosilanes such as tetrachlorosilane, tetrabromosilane,tetraiodosilane, trichlorobromosilane and dichlorodibromosilane;monoalkyltrihalogenosilanes such as methyltrichlorosilane,methyldichlorobromosilane and cyclohexyltrichlorosilane;monoaryltrihalogenosilanes such as phenyltrichlorosilane,naphthyltrichlorosilane, 4-chlorophenyltrichlorosilane andphenyldichlorobromosilane; monoaryloxytrihalogenosilanes such asphenoxytrichlorosilane and phenoxydichlorobromosilane;monoalkoxytrihalogenosilanes such as methoxytrichlorosilane andethoxytrichlorosilane; dialkyldihalogenosilanes such asdimethyldichlorosilane, methyl(ethyl)dichlorosilane andmethyl(cyclohexyl)dichlorosilane; monoalkylmonoaryldihalogenosilanessuch as methyl(phenyl)dichlorosilane; diaryldihalogenosilanes such asdiphenyldichlorosilane; diaryloxydihalogenosilanes such asdiphenoxydichlorosilane; monoalkylmonoaryloxydihalogenosilanes such asmethyl(phenoxy)dichlorosilane; monoarylmonoaryloxydihalogenosilanes suchas phenyl(phenoxy)dichlorosilane; dialkoxydihalogenosilanes such asdiethoxydichlorosilane; monoalkylmonoalkoxydichlorosilanes such asmethyl(ethoxy)dichlorosilane; monoarylmonoethoxydichlorosilanes such asphenyl(ethoxy)dichlorosilane; trialkylmonohalogenosilanes such astrimethylchlorosilane, dimethyl(ethyl)chlorosilane anddimethyl(cyclohexyl)chlorosilane; dialkylmonoarylmonohalogenosilanessuch as dimethyl(phenyl)chlorosilane; monoalkyldiarylmonohalogenosilanessuch as methyl(diphenyl)chlorosilane; triaryloxymonohalogenosilanes suchas triphenoxychlorosilane; monoalkyldiaryloxymonohalogenosilanes such asmethyl(diphenoxy)chlorosilane; monoaryldiaryloxymonohalogenosilanes suchas phenyl(diphenoxy)chlorosilane; dialkylmonoaryloxymonohalogenosilanessuch as dimethyl(phenoxy)chlorosilane;diarylmonoaryloxymonohalogenosilanes such asdiphenyl(phenoxy)chlorosilane;monoalkylmonoarylmonoaryloxymonohalgenosilanes such asmethyl(phenyl)(phenoxy)chlorosilane; triethoxymonohalogenosilanes suchas triethoxychlorosilane; and oligomers of the above compounds such asdimers, trimers, tetramers and pentamers of tetrachlorosilane.

[0157] Examples of the above other silyl compound includehexamethyldisilazane, t-butyldimethylchlorosilane,bis(trimethylsilyl)trifluoroacetamide, diethylaminotrimethylsilane,trimethylsilanol, hexamethyldisiloxane,chloromethyldimethylethoxysilane, acetyltriphenylsilane,ethoxytriphenylsilane, triphenylsilanol, triethylsilanol,tripropylsilanol, tributylsilanol, hexaethyldisiloxane,trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane,triethylethoxysilane, acetoxyethyldimethylchlorosilane,1,3-bis(hydroxybutyl)tetramethyldisiloxane,1,3-bis(hydroxypropyl)tetramethyldisiloxane, γ-aminopropylmethoxysilane,γ-aminopropylethoxysilane,N-β(aminoethyl)-γ-aminopropyltrimethoxysilane,N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane,N-phenyl-γ-aminopropyltrimethoxysilane, γ-anilinopropyltrimethoxysilane,γ-dibutylaminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane,N-β(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane.hydrochlorate,γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane,vinyltriethoxysilane, vinyltrichlorosilane,vinyltris(β-methoxyethoxy)silane, γ-glycidoxypropylmethyldiethoxysilane,γ-glycidoxypropyltriethoxysilane,γ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,γ-chloropropyltrimethoxysilane, trimethylchlorosilane,hexamethyldisilazane, N-trimethylsilylimidazole,bis(trimethylsilyl)urea, trimethylsilylacetamide,bistrimethylsilylacetamide, trimethylsilylisocyanate,trimethylmethoxysilane, trimethylethoxysilane, methyltrimethoxysilane,methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane,t-butyldimethylchlorosilane, t-butyldiphenylchlorosilane,triisopropylchlorosilane, n-propyltrimethoxysilane,isobutyltrimethoxysilane, n-hexyltrimethoxysilane,n-decyltrimethoxysilane, n-hexadecyltrimethoxysilane,1,6-bis(trimethoxysilyl)hexane, dimethylsilyldiisocyanate,methylsilyltriisocyanate, phenyltrimethoxysilane,diphenyldimethoxysilane and phenylsilyltriisocyanate.

[0158] Out of these, the stabilizer (D) used in the present invention ispreferably an amino compound, epoxy compound, thiirane compound, oxetanecompound, oxazoline compound, oxazine compound, silyl compound,isocyanate compound or cyanate compound, more preferably an aminocompound, epoxy compound, thiirane compound, oxetane compound, oxazolinecompound or oxazine compound. It is particularly preferablyethylenediamine, phenylglycidyl ether, 3-phenoxypropylene sulfide,3,3,3-trifluoropropylene oxide, hexamethyldisilazane,γ-aminopropylmethoxysilane, γ-glycidoxypropyltrimethoxysilane ormethylsilyltriisocyanate.

[0159] These stabilizers (D) may be used alone or in combination of twoor more. The amount of the component (D) may be excessive so that theresidual decomposable compound (A) can react to the full but it isgenerally 10 parts or more by weight, preferably 30 parts or more byweight based on 100 parts by weight of the component (A). When theamount of the component (D) is smaller than 10 parts by weight, thestability of the dielectric constant changing material may becomeunsatisfactory due to an incomplete reaction.

[0160] A catalyst may be used in combination with the stabilizer (D).Use of the catalyst promotes a reaction between the component (D) andthe residual decomposable compound (A).

[0161] The catalyst is, for example, an acid catalyst, basic catalyst orquaternary onium salt.

[0162] Examples of the above acid catalyst include organic acids such asacetic acid, methanesulfonic acid, p-toluenesulfonic acid,trifluoroacetic acid and trifluoromethanesulfonic acid; and inorganicacids such as hydrochloric acid, sulfuric acid and nitric acid. Examplesof the above basic catalyst include alkali metal carbonates such assodium carbonate, potassium carbonate and lithium carbonate; alkalimetal bicarbonates such as sodium bicarbonate, potassium bicarbonate andlithium bicarbonate; alkali metal acetates such as sodium acetate;alkali metal hydrides such as lithium hydride, sodium hydride andpotassium hydride; alkali metal hydroxides such as sodium hydroxide,potassium hydroxide and lithium hydroxide; alkali metal alkoxides suchas sodium methoxide, sodium ethoxide, potassium t-butoxide and lithiummethoxide; mercaptan alkali metals such as methyl mercaptan sodium andethyl mercaptan sodium; organic amines such as triethylamine,tributylamine, diisopropylethylamine, N-methylmorpholine, pyridine,4-(N,N-dimethylamino)pyridine, N,N-dimethylaniline, N,N-diethylaniline,1,5-diazabicyclo[4.3.0]non-5-ene, 1,4-diazabicyclo[2.2.2]octane (DABCO)and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); alkyl lithiums such asmethyl lithium, ethyl lithium and butyl lithium; and lithium alkylamides such as lithium diisopropylamide and lithium dicyclohexylamide.Examples of the above quaternary onium salt include tetrabutylammoniumchloride, tetrabutylammonium bromide, tetrabutylammonium iodide,tetrabutylammonium acetate, tetrabutylphosphonium chloride,tetrabutylphosphonium bromide, cetyltrimethylammonium bromide,tetrapropylammonium bromide and benzyltriethylammonium chloride. Acombination of 18-crown-6-ether and a salt such as potassium chloride,potassium bromide, potassium iodide, cesium chloride, potassiumphenoxide, sodium phenoxide or potassium benzoate may also be used as acatalyst.

[0163] Out of these, p-toluenesulfonic acid, hydrochloric acid, sulfuricacid, sodium hydroxide, potassium t-butoxide, triethylamine, DBU,tetrabutylammonium bromide, tetrabutylphosphonium bromide and18-crown-6-ether/potassium phenoxide are preferred as a catalyst.

[0164] The amount of the catalyst is preferably 2 mols or less based on1 equivalent of the component (D) when an amino compound, alkoxymethylmelamine compound, alkoxymethyl glycoluril compound, alkoxymethylbenzoguanamine compound, alkoxymethyl urea compound or halogenated silylcompound is used as the component (D).

[0165] When an epoxy compound, thiirane compound, oxetane compound,isocyanate compound, cyanate compound, oxazoline compound, oxazinecompound or other silyl compound is used as the component (D), theamount of the catalyst is preferably 0.2 mol or less based on 1equivalent of the component (D).

[0166] The number of equivalents of the component (D) is obtained bymultiplying the number of reactive groups contained in the component (D)by the amount (mol) of the component (D), and the number of reactivegroups is defined as follows according to the type of the component (D).amino compound: number of nitrogen atoms epoxy compound: number of epoxygroups thiirane compound: number of ethylene sulfide groups oxetanecompound: number of oxetanyl groups alkoxymethyl melamine compound,alkoxymethyl glycoluril compound, alkoxymethyl benzoguanamine compoundand alkoxymethyl urea compound: number of alkoxymethyl groups isocyanatecompound: number of isocyanate groups cyanate compound: number ofcyanate groups oxazoline compound: number of oxazolyl groups oxazinecompound: number of oxazyl groups halogenated silyl compound: number ofhalogen atoms bonded to silicon atoms other silyl compound: number ofsilicon atoms

[0167] <Other Components>

[0168] The dielectric constant changing composition used in the presentinvention may contain other additives in limits not prejudicial to theobject of the present invention. The additives include an ultravioletlight absorber, sensitizer, surfactant, heat resistance improving agentand adhesive aid.

[0169] The above ultraviolet light absorber is selected from abenzotriazole, salicylate, benzophenone, substituted acrylonitrile,xanthene, coumarin, flavone and chalcone. Specific examples of theultraviolet light absorber include Tinubin 234(2-(2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl)-2H-benzotriazole),Tinubin 571 (hydroxyphenylbenzotriazole derivative) and Tinubin 1130(condensate ofmethyl-3-(3-t-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl)propionateand polyethylene glycol (molecular weight of 300)) (of Ciba SpecialtyChemicals Co., Ltd.),1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadien-3,5-dione, anddibenzylidene acetone.

[0170] By adding an ultraviolet light absorber, the amount of an acid orbase formed from the component (C) can be made gradually smaller as thedepth from the surface of an exposed portion of the dielectric constantchanging composition of the present invention increases. The amount ofthe ultraviolet light absorber is preferably 30 parts or less by weight,more preferably 20 parts or less by weight based on 100 parts by weightof the total of the components (A) and (B).

[0171] The above sensitizer is selected from a coumarin having asubstituent at the 3-position and/or 7-position, flavone,dibenzalacetone, dibenzalcyclohexane, chalcone, xanthene, thioxanthene,porphyrin, phthalocyanine, acridine and anthracene.

[0172] The amount of the sensitizer is preferably 30 parts or less byweight, more preferably 20 parts or less by weight based on 100 parts byweight of the total of the components (A) and (B).

[0173] The above surfactant may be added to improve coatability, forexample, prevent striation, and improve developability.

[0174] Examples of the surfactant include nonionic surfactants such aspolyoxyethylene alkyl ethers including polyoxyethylene lauryl ether,polyoxyethylene stearyl ether and polyoxyethylene oleyl ether,polyoxyethylene aryl ethers including polyoxyethylene octylphenyl etherand polyoxyethylene nonylphenyl ether, and polyethylene glycol dialkylesters including polyethylene glycol dilaurate and polyethylene glycoldistearate; fluoro-based surfactants commercially available under thetrade names of F Top EF301, EF303 and EF352 (of Shin Akita Kasei Co.,Ltd.), Megafac F171, F172 and F173 (of Dainippon Ink and Chemicals,Inc.), Florade FC430 and FC431 (of Sumitomo 3M Limited), and Asahi GuardAG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106(of Asahi Glass Co., Ltd.); and other surfactants commercially availableunder the trade names of organosiloxane polymer KP341 (of Shin-EtsuChemical Co., Ltd.) and acrylic or methacrylic acid-based (co)polymerPolyflow No. 57 and No. 95 (of Kyoeisha Kagaku Co., Ltd.).

[0175] The amount of the surfactant is preferably 2 parts or less byweight, more preferably 1 part or less by weight based on 100 parts byweight of the total of the components (A) and (B).

[0176] The above adhesive aid may be added to improve adhesion to asubstrate and is preferably a silane coupling agent.

[0177] The above heat resistance improving agent is an unsaturatedcompound such as a polyvalent acrylate.

[0178] An antistatic agent, keeping stabilizer, halation inhibitor,anti-foaming agent, pigment and thermal acid generator may be furtheradded to the dielectric constant changing material used in the presentinvention, as required.

[0179] <Formation of Dielectric Constant Pattern>

[0180] In the present invention, a dielectric constant pattern can beformed from the above dielectric constant changing composition asfollows, for example.

[0181] First, the dielectric constant changing composition is dissolvedor dispersed in a solvent to prepare a composition solution having asolid content of 5 to 70 wt %. The composition solution may be filteredwith a filter having an opening diameter of about 0.1 to 10 μm asrequired before use.

[0182] Thereafter, this composition solution is applied to the surfaceof a substrate such as a silicon wafer and prebaked to remove thesolvent so as to form the coating film of the dielectric constantchanging composition. Part of the formed coating film is then exposed toradiation through a pattern mask and heated to form pores in the exposedportion of the coating film and solidify the film so as to produce adielectric constant difference between the exposed and unexposedportions of the dielectric constant changing composition.

[0183] An acid or base is formed from the radiation sensitive decomposer(C) by the above exposure to act on the component (A) to decompose it.When this decomposed product is gaseous at normal temperature, itdissipates at the time of heating after exposure to form pores.

[0184] When the decomposed product is liquid or solid at normaltemperature, it is vaporized or sublimated as a gas by heating at atemperature raised at the time of heating to be dissipated so as to formpores, or only the decomposed product is extracted to form pores. As aresult, there is produced a dielectric constant difference between theexposed and unexposed portions.

[0185] When the component (D) to be reacted with the residual component(A) which did not react with an acid or base is not existent at the timeof heating, heating is further carried out to decompose the residualcomponent (A). Heating is preferably carried out in such a manner thatpores are not formed by the decomposed product.

[0186] When the component (D)is existent at the time of heating, theresidual component (A) which did not react with the acid or base reactswith the component (D) to stabilize the formed dielectric constantpattern.

[0187] The solvent used to prepare a solution containing the dielectricconstant changing composition used in the present invention uniformlydissolves the above components (A), (B) and (C), the optionally addedcomponent (D) and other additives and does not react with thesecomponents.

[0188] Illustrative examples of the solvent include alcohols such asmethanol, ethanol, propanol, iso-propanol, butanol, ethylene glycol andpropylene glycol; ethers such as tetrahydrofuran; glycol ethers such asethylene glycol monomethyl ether and ethylene glycol monoethyl ether;ethylene glycol alkylether acetates such as methyl cellosolve acetateand ethyl cellosolve acetate; diethylene glycols such as diethyleneglycol monomethyl ether, diethylene glycol monoethyl ether, diethyleneglycol dimethyl ether and diethylene glycol ethyl methyl ether;propylene glycol monoalkyl ethers such as propylene glycol methyl ether,propylene glycol ethyl ether, propylene glycol propyl ether andpropylene glycol butyl ether; propylene glycol alkyl ether acetates suchas propylene glycol methyl ether acetate, propylene glycol ethyl etheracetate, propylene glycol propyl ether acetate and propylene glycolbutyl ether acetate; propylene glycol alkyl ether propionates such aspropylene glycol methyl ether propionate, propylene glycol ethyl etherpropionate, propylene glycol propyl ether propionate and propyleneglycol butyl ether propionate; aromatic hydrocarbons such as toluene andxylene; ketones such as methyl ethyl ketone, cyclohexanone and4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethylacetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate,methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate,methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate,methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl3-hydroxypropionate, butyl 3-hydroxypropionate, methyl2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethylmethoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methylethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butylethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethylbutoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl2-methoxypropionate, ethyl 2-methoxypropionate, propyl2-methoxypropionate, butyl 2-methoxypropionate, methyl2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate,butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate,methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl3-methoxypropionate, butyl 3-methoxypropionate, methyl3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate,butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl3-propoxypropionate, propyl 3-propoxypropionate, butyl3-propoxypropionate, methyl 3-butoxypropionate, ethyl3-butoxypropionate, propyl 3-butoxypropionate and butyl3-butoxypropionate; and fluorine atom-containing solvents such astrifluoromethylbenzene, 1,3-bis(trifluoromethyl)benzene,hexafluorobenzene, hexafluorocyclohexane, perfluorodimethylcyclohexane,perfluoromethylcyclohexane, octafluorodecaline and1,1,2-trichloro-1,2,2-trifluoroethane.

[0189] Out of these solvents, alcohols, glycol ethers, ethylene glycolalkyl ether acetates, propylene glycol alkyl ether acetates, ketones,esters and diethylene glycols are preferred from the viewpoints ofsolubility, reactivity with each component and ease of forming a coatingfilm.

[0190] Further, a high-boiling solvent may be used in combination withthe above solvent. Examples of the high-boiling solvent includeN-methylformamide, N,N-dimethylformamide, N-methylformanilide,N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone,isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzylalcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethylmaleate, γ-butyrolactone, ethylene carbonate, propylene carbonate andphenyl cellosolve acetate.

[0191] The dielectric constant changing composition used in the presentinvention is formed into various shapes in consideration of applicationpurpose before exposure to radiation. For example, it is formed like arod, fiber, long board, sphere, film or lens and the present inventionis not limited to these. A commonly used molding technique may be used,as exemplified by injection molding, compression molding, blow molding,extrusion, in-case frame polymerization, shaving, drawing,heating/cooling, CVD deposition, sintering and scanning. Spin coating,slitting, bar coating, solvent casting, LB, spraying, roll coating,relief-printing or screen printing may also be used according to theapplication purpose of an optically molded product.

[0192] In this molding process, heating (to be referred to as“prebaking” hereinafter) is preferably carried out. The heatingcondition which changes according to the composition of the material ofthe present invention and the type of each additive is preferably 30 to200° C., more preferably 40 to 150° C. A hot plate or oven, or infraredradiation may be used for heating.

[0193] The radiation used for exposure is an i-line having a wavelengthof 365 nm, h-line having a wavelength of 404 nm, g-line having awavelength of 436 nm, ultraviolet radiation from a wide-range wavelengthlight source such as a xenon lamp, far ultraviolet radiation such as KrFexcimer laser beam having a wavelength of 248 nm or ArF excimer laserbeam having a wavelength of 193 nm, X-radiation such as synchrotronradiation, charged corpuscular beam such as electron beam, visibleradiation or a mixture thereof. Out of these, ultraviolet radiation andvisible radiation are preferred. The illuminance which depends on thewavelength of the radiation is preferably 0.1 to 100 mW/cm² because thehighest reaction efficiency is obtained. The projection of the radiationthrough a pattern mask makes possible the patterning of the radiationsensitive dielectric constant changing material. As for patterningaccuracy which is affected by a light source used, a dielectric constantpattern having a dielectric constant variation distribution with aresolution of about 0.2 μm can be produced.

[0194] In the present invention, heating (to be referred to as“post-exposure baking (PEB)”) is preferably carried out after exposure.A similar device to the above prebaking device may be used for PEB andPEB conditions may be arbitrary. The heating temperature is preferably30 to 150° C., more preferably 30 to 130° C. Heating is preferablycarried out for stabilization, that is, a reaction between the residualcomponent (A) and the component (D) successively after post-exposurebaking or separately. The heating temperature for stabilization ispreferably 35 to 200° C., more preferably a temperature 10° C. or morehigher than the PEB temperature, much more preferably a temperature 20°C. or more higher than the PEB temperature.

[0195] Further, re-exposure may be carried out to decompose the residualcomponent (C) existent in the unexposed portion and further improve thestability of the material.

[0196] The re-exposure may be carried out by applying radiation havingthe same wavelength as the radiation used to change the dielectricconstant to the entire surface of the pattern in the same amount.

[0197] Optionally, heating may be further carried out to further improvethe stability of the material. A similar device to the prebaking deviceused at the time of molding the material may be used for heating and theheating conditions may be arbitrary.

[0198] According to the present invention, the method of forming adielectric constant pattern of the present invention may also be carriedout by exposing a dielectric constant changing composition comprisingthe above components (A), (B) and (C) to radiation through a patternmask and then treating it with the stabilizer (D).

[0199] The treatment with the stabilizer (D) is preferably carried outafter post-exposure baking.

[0200] The stabilizer (D) has the function of stabilizing the residualdecomposable compound (A) contained in the dielectric constant changingmaterial after exposure to provide stability to an acid or base. Thisstabilization prevents a change in dielectric constant and hence thedeterioration of a dielectric constant pattern formed by the method ofthe present invention even when it is used under the condition thatlight having a wavelength close to the wavelength used to change thedielectric constant passes therethrough.

[0201] Besides the above examples, a low-boiling compound such asammonia or triethylamine may be used as the stabilizer (D).

[0202] For contact between the dielectric constant changing materialafter exposure to radiation and the stabilizer (D) for stabilization, asuitable method may be employed. For instance, the component (D) andoptionally a catalyst are dissolved in a suitable solvent to becontacted to the dielectric constant changing material as a solution.Alternatively, when the component (D) is liquid or gaseous under contactconditions, it may be 100% directly contacted to the dielectric constantchanging material.

[0203] When a solvent is used in the reaction between the abovestabilizer (D) and the component (A), the solvent preferably dissolvesthe component (D) and an optionally added catalyst and does not dissolvethe component (A). If the above solvent is selected, the surface of theobtained dielectric constant pattern will not be roughened.

[0204] Examples of the solvent include water; alcohols such as methanol,ethanol, iso-propanol, n-propanol, n-butanol, iso-butanol, tert-butanol,cyclohexanol, ethylene glycol, propylene glycol and diethylene glycol;ethers such as diethyl ether and tetrahydrofuran; glycol ethers such asethylene glycol monomethyl ether and ethylene glycol monoethyl ether;ethylene glycol alkyl ether acetates such as methyl cellosolve acetateand ethyl cellosolve acetate; diethylene glycols such as diethyleneglycol monomethyl ether, diethylene glycol monoethyl ether anddiethylene glycol dimethyl ether; propylene glycol monoalkyl ethers suchas propylene glycol methyl ether and propylene glycol ethyl ether;propylene glycol alkyl ether acetates such as propylene glycol methylether acetate and propylene glycol ethyl ether acetate; propylene glycolalkyl ether propionates such as propylene glycol methyl etherpropionate, propylene glycol ethyl ether propionate, propylene glycolpropyl ether propionate and propylene glycol butyl ether propionate;aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbonssuch as n-hexane, n-heptane and n-octane; ketones such as methyl ethylketone, cyclohexanone, methyl isobutyl ketone, methylamyl ketone and4-hydroxy-4-methyl-2-pentanone; esters such as ethyl acetate, propylacetate, butyl acetate, ethyl 2-hydroxypropionate, methyl2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, butylhydroxyacetate, ethyl lactate, propyl lactate, butyl lactate, methyl3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, ethylmethoxyacetate, butyl methoxyacetate, ethyl 2-methoxypropionate, butyl2-methoxypropionate, butyl 2-ethoxypropionate, butyl 2-butoxypropionate,butyl 3-methoxypropionate, butyl 3-ethoxypropionate, butyl3-propoxypropionate and butyl 3-butoxypropionate; and fluorineatom-containing solvents such as trifluoromethylbenzene,1,3-bis(trifluoromethyl)benzene, hexafluorobenzene,hexafluorocyclohexane, perfluorodimethylcyclohexane,perfluoromethylcyclohexane, octafluorodecalin and1,1,2-trichloro-1,2,2-trifluoroethane.

[0205] Out of these solvents, water, alcohols, glycol ethers, ethyleneglycol alkyl ether acetates and fluorine atom-containing solvents arepreferred.

[0206] The reaction temperature for carrying out a reaction between thestabilizer (D) and the residual decomposable compound (A) is generally 0to 130° C., and the reaction time is generally 10 seconds to 1 hour.

[0207] Further, re-exposure may be carried out to decompose the residualcomponent (C) existent in the unexposed portion and further improve thestability of the material.

[0208] As for which is not described of the dielectric constant patternforming method including the above stabilization, it should beunderstood that what is described of the above dielectric constantpattern forming method is applied directly or with modifications obviousto one of ordinary skill in the art.

[0209] Further, according to the present invention, the dielectricconstant pattern forming method of the present invention may also becarried out by exposing a dielectric constant changing compositioncomprising the above components (A), (B) and (C) to radiation through apattern and heating it to decompose the decomposable compound in theunexposed portion.

[0210] The above heating is preferably carried out at a temperature 10°C. or more higher than the post-exposure baking temperature, forexample, 170° C. or higher, more preferably 200° C. or higher.

[0211] The residual decomposable compound (A) existent in the unexposedportion is decomposed or sublimated by heating to be removed but itpreferably does not form pores substantially.

[0212] As for what is not described of the above dielectric constantpattern forming method when the component (D) is not contained, itshould be understood that relevant items out of what is described of theabove pattern forming method are applied directly or with modificationsobvious to one of ordinary skill in the art.

[0213] In the dielectric constant pattern of the present inventionformed as described above, the dielectric constant of the exposedportion is preferably lower than the dielectric constant of theunexposed portion. More preferably, the dielectric constant of theexposed portion is 90% or less, preferably 75% or less of the dielectricconstant of the unexposed portion.

[0214] The porosity of the exposed portion is preferably 10 to 99.9%,more preferably 15 to 99.9%, particularly preferably 20 to 99.9%.

[0215] Further, the elastic moduli of the exposed portion and theunexposed portion are preferably 0.3 GPa or more and 1 GPa or more, morepreferably 0.5 GPa or more and 3 GPa or more, respectively.

[0216] As described above, the composition of the present invention isformed into a film and a pattern consisting of a plurality of regionshaving different dielectric constants can be formed. Therefore, when afilm whose necessary portion has a low dielectric constant is used as aninsulating material for a circuit board, the strength of the film can begreatly made higher than a conventional organic insulating materialhaving a low dielectric constant and pores on whole of the film.

[0217] The composition of the present invention can be suitably used asan interlayer insulating film between multi-layer wiring patterns.

[0218] Further, the dielectric constant pattern formed from thecomposition of the present invention can be used as a capacitor and alsoas an input/output capacitor or path capacitor to be mounted on an LSIhaving built-in passive elements or a substrate having built-in passiveelements. When the composition of the present invention is used as acapacitor, the capacitor can be made lighter and thinner than acapacitor made from a conventionally known material and can have adesired shape, thereby making it possible to increase the capacity pervolume and the degree of freedom in the design of an array when passiveelements are disposed in an array.

EXAMPLES

[0219] The following examples are provided for the purpose of furtherillustrating the present invention but are in no way to be taken aslimiting.

[0220] In the following examples, the weight average molecular weight interms of polystyrene of each compound was measured with the GPCCHROMATOGRAPH SYSTEM-21 of Showa Denko K.K.

Synthesis Examples of Component (A) Synthesis Example 1 of Component (A)

[0221] 49.84 g of terephthalic acid and 57.34 g ofphenylmethyldichlorosilane were dissolved in 200 g ofN-methylpyrrolidone in a 500 ml three-necked flask in an argonatmosphere. A solution prepared by dissolving 23.73 g of pyridine in 50g of N-methylpyrrolidone was added to the above solution under agitationand cooling with ice over 1 hour. After addition, the reaction solutionwas heated at 60° C. to carry out polymerization for 24 hours. After theend of polymerization, the reaction solution was poured into 2 liters ofmethanol to precipitate a polymer which was then dissolved in 200 ml ofN-methylpyrrolidone and added to 2 liters of methanol for purificationby re-precipitation.

[0222] The precipitated compound was separated by filtration and driedunder vacuum at 50° C. to obtain 70.80 g of a compound (A-1). The weightaverage molecular weight of the obtained compound was 26,000.

Synthesis Example 2 of Component (A)

[0223] 50 g of o-phthalaldehyde and 500 g of tetrahydrofuran as monomerswere fed to a 1 liter flask the inside of which was then substituted bynitrogen and cooled to −78° C. 41.83 g of tert-butoxypotassium was addedto the mixture and stirred under cooling at −78° C. in a nitrogenatmosphere for 48 hours.

[0224] 45.67 g of acetic anhydride and 35.38 g of pyridine were added tothe obtained reaction solution under cooling and stirred at −78° C. for2 hours. The reaction solution was concentrated to 100 ml by heating at60° C. under reduced pressure, dissolved in 1 liter of ethyl acetate andwashed with ion exchange water three times, ethyl acetate wasconcentrated, and the reaction solution was vacuum dried at 50° C. toobtain 45 g of a compound (A-2). It was found from ¹H-NMR that the ratioof a t-butyl group derived from tert-butoxypotassium to an aromaticgroup derived from o-phthalaldehyde was 1:1 based on the integral ratioof a proton derived from 1.2 to 1.3 ppm of a tert-butyl group to aproton derived from 7.2 to 7.7 ppm of an aromatic group.

Synthesis Example 3 of Component (A)

[0225] 49.84 g of terephthalic acid chloride was dissolved in 150 ml ofchloroform in a 500 ml three-necked flask in an argon atmosphere, and asolution prepared by dissolving 33.05 g of 1,4-benzenethiol and 16.83 gof potassium hydroxide in 150 ml of ion exchange water was added to theabove obtained solution and stirred to carry out interfacialpolycondensation. After 4 hours of the reaction, the reaction productwas purified by re-precipitation with tetrahydrofuran-methanol twice.

[0226] The precipitated compound was separated by filtration and vacuumdried at 50° C. to obtain 56.55 g of a compound (A-3). The weightaverage molecular weigh of the obtained compound was 7,600.

Synthesis Example 4 of Component (A)

[0227] 8 g of 2,2′-azobis(2,4-dimethylvaleronitrile) and 200 g ofdiethylene glycol dimethyl ether were fed to a 500 ml three-neckedflask. After 100 g of tert-butyl methacrylate was fed to the flask andthe inside of the flask was substituted by nitrogen, stirring wasstarted gently. The temperature of the solution was raised to 90° C. andmaintained at that temperature for 3 hours to obtain a solution of apolymer (A-4). The solid content of the obtained polymer solution was31.0 wt % and the weight average molecular weight of the polymer was5,500.

Synthesis Examples of Component (B) Synthesis Example 1 of Component (B)

[0228] 50 g of methyltrimethoxysilane was placed in a 1 literthree-necked flask, 100 g of 1-ethoxy-2-propanol was added to the flaskto be dissolved, and the obtained mixed solution was heated at 60° C.under agitation with a magnetic stirrer. 19.85 g of ion exchange waterwas added to this continuously over 1 hour. A reaction was carried outat 60° C. for 4 hours, and the obtained reaction solution was cooled toroom temperature.

[0229] Thereafter, methanol which was a reaction by-product wasdistilled off from the reaction solution under reduced pressure, and theresidue was concentrated to a solid content of 20 wt % to obtain asolution containing a compound. (B-1). The weight average molecularweight of the compound (B-1) was 2,200.

Synthesis Example 2 of Component (B)

[0230] 200 g of tetrabutoxytitanium was dissolved in anhydrous toluenein a 1 liter three-necked flask to prepare a solution which was thenheated at 85° C. A mixed solution of 20.1 g of ion exchange water and400 g of n-butyl alcohol was added dropwise to this solution at 85° C.over 1 hour. After the end of addition, the resulting solution wasfurther heated at 85° C. for 3 hours under agitation. The thus obtainedreaction solution was heated at 150° C. under reduced pressure (0.1mmHg) to distill off a volatile component. Subsequently, 500 g of1-ethoxy-2-propanol was added to the reaction solution which was thenconcentrated to a solid content of 20 wt % to obtain a solutioncontaining a compound (B-1). The weight average molecular weight of thiscompound (B-2) was 2,200.

Example 1

[0231] 50 parts by weight of the compound (A-1) as the component (A), asolution containing the compound (B-1) (corresponding to 50 parts byweight (solid content) of the compound (B-1)) as the component (B) and 1part by weight of 4-phenylthiophenyldiphenylsulfoniumtrifluoromethanesulfonato as the component (C) were dissolved indiethylene glycol ethyl methyl ether to a total solid content of 20 wt%, and the resulting solution was filtered with a membrane filter havingan opening diameter of 0.2 μm to prepare a solution of a dielectricconstant changing material.

[0232] (1) Formation of a Coating Film

[0233] The above solution was applied to a silicon substrate with aspinner and prebaked on a hot plate at 130° C. for 2 minutes to form a1.0 μm-thick coating film.

[0234] (2) Formation of a Dielectric Constant Pattern

[0235] The coating film obtained as described above was exposed to 50mJ/cm² of radiation with the NSR1505i6A reduction projection exposuredevice (of Nikon Corporation, NA=0.45, λ=365 nm) at the optimum focusingdepth. The coating film was then baked at 100° C. for 2 minutes afterexposure to form a dielectric constant pattern having a dielectricconstant difference between exposed and unexposed portions. A portionexposed to radiation of the dielectric constant pattern formed hereinwill be referred to as “exposed portion” and a portion unexposed toradiation will be referred to as “unexposed portion” hereinafter.

[0236] (3) Stabilization

[0237] 150 ml of phenyl glycidyl ether (containing 0.1 mmol oftetrabutylammonium bromide as a reaction catalyst) as the component (D)was heated at 100° C., and the dielectric constant patterns formed on asilicon substrate and a glass substrate formed as described above wereimmersed in the component (D) at 100° C. for 2 minutes and rinsed withsuper pure water for 1 minute.

[0238] Then, the entire surfaces of the patterns were re-exposed to 4.5mW/cm² of radiation using the Canon PLA-501F for 1 minute without afilter and heated in an oven at 200° C. for 10 minutes to stabilize thedielectric constant patterns.

[0239] (4) Measurement of Surface Area by BET Method

[0240] The surface areas of the exposed portion and unexposed portion ofthe dielectric constant pattern formed as described above were measuredby a BET method using the OMNISORP 100/360 SERIES of COULTER Co., Ltd.

[0241] (5) Measurement of Porosity by Mercury Porosimeter

[0242] The porosities of the exposed portion and unexposed portion ofthe dielectric constant pattern formed as described above were measuredby a mercury porosimeter (Auto Pore 9200 of Shimadzu Corporation havinga minimum measurable pore dieter of 34 Å).

[0243] (6) Measurement of Pore Distribution by BJH Method

[0244] The pore distributions of the exposed and unexposed portions ofthe dielectric constant pattern formed as described above were measuredby a BJH method using the OMNISORP 100/360 SERIES of COULTER Co., Ltd.The number of pores having a diameter of 100 nm or more per 1 mm³ isshown in Table 2.

[0245] (7) Measurement of Pore Diameter by Observation through ElectronMicroscope

[0246] The number of pores having a diameter of 100 nm or more per 10μm² in an arbitrary observation range was counted in the measurement ofpore distributions of the exposed and unexposed portions of thedielectric constant pattern formed above by observation through atransmission electron microscope.

[0247] (8) Measurement of Refractive Index

[0248] The refractive indices of the exposed and unexposed portions ofthe dielectric constant pattern formed above were measured by the AutoEL IV NIR III elipsometer (of Rudolf Research Co., Ltd.) at 633 nm. Theresults are shown in Table 1.

[0249] (9) Elastic Modulus (Young's Modulus)

[0250] This was measured by a continuous stiffness measuring methodusing the Nano Indenter XP (of Nano Instrument Co., Ltd.).

[0251] (10) Dielectric Constant

[0252] An aluminum electrode pattern was formed on the obtained film bya deposition method to prepare a sample for the measurement ofdielectric constant. The sample was used for the measurement of thedielectric constant of the coating film by a CV method at a frequency of100 kHz using the HP16451B electrode and HP4284A precision LCR meter ofYokagawa Hewlett Packard Co., Ltd.

Example 2

[0253] Evaluations were carried out in the same manner as in Example 1except that 50 parts by weight of the compound (A-2) was used as thecomponent (A), the post-exposure baking temperature in the step (2)(formation of dielectric constant pattern) was changed as shown in Table1, and the type of the component (D) and the stabilization temperaturein the step (3) (stabilization) were changed as shown in Table 2. Theresults are shown in Table 1 and Table 2.

Example 3

[0254] Evaluations were carried out in the same manner as in Example 1except that 50 parts by weight of the compound (A-3) was used as thecomponent (A), 5 parts by weight ofN-(2-nitrobenzyloxycaronyl)pyrrolidine was used as the component (C),the dosage of radiation in step (2) (formation of dielectric constantpattern) was changed as shown in Table 1, and the type of the component(D) in the step (3) (stabilization) was changed as shown in Table 2. Theresults are shown in Table 1 and Table 2.

Example 4

[0255] Evaluations were carried out in the same manner as in Example 1except that a solution containing the compound (B-2) (corresponding to50 parts by weight (solid content) of the compound (B-2)) was used asthe component (B). The results are shown in Table 1 and Table 2.

Example 5

[0256] Evaluations were carried out in the same manner as in Example 1except that 50 parts by weight of the compound (A-4) was used as thecomponent (A), the post-exposure baking temperature in the step (2)(formation of dielectric constant pattern) was changed as shown in Table1, the coating film was immersed in a 2.38% aqueous solution oftetramethylammonium hydroxide for 1 minute before stabilization toextract the component A, and the type of the component (D) and thestabilization temperature in the step (3) (stabilization) were changedas shown in Table 2. The results are shown in Table 1 and Table 2.

Example 6

[0257] The procedure of Example 1 was repeated up to the step (2)(formation of dielectric constant pattern) and then baking was carriedout at 200° C. for 5 minutes without stabilization and further at 350°C. for 1 hour. The steps (4) to (10) were the same as in Example 1. Theresults are shown in Table 1 and Table 2. TABLE 1 Conditions for forminga dielectric constant pattern Post-exposure Stabilization conditionsDosage baking temperature Type of (mJ/cm²) (° C.) component (D)Temperature Ex. 1 80 100 D-1 80 Ex. 2 60 100 D-2 20 Ex. 3 100 100 D-1 80Ex. 4 100 100 D-1 80 Ex. 5 80 150 D-1 80 Ex. 6 80 100 none 80

[0258] In Table 1, symbols for the component (D) indicate the following.

[0259] D-1; phenylglycidyl ether (containing 10 mol % oftetrabutylammonium bromide)

[0260] D-2; 1% aqueous solution of p-xylylenediamine TABLE 2 Number ofpores having a diameter of 100 nm Surface area Porosity or more inexposed portion Exposed Unexposed Exposed Unexposed BJH Observationthrough electron portion portion portion portion method microscope Ex. 1510 m²/g —¹⁾ 28% 0% 0 0 Ex. 2 700 m²/g —¹⁾ 38% 0% 0 0 Ex. 3 450 m²/g —¹⁾22% 0% 0 0 Ex. 4 450 m²/g —¹⁾ 21% 0% 0 0 Ex. 5 500 m²/g —¹⁾ 25% 0% 0 0Ex. 6 520 m²/g —¹⁾ 28% 0% 0 0 Refractive index Elastic modulusDielectric constant Exposed Unexposed Exposed Unexposed ExposedUnexposed portion portion portion portion portion portion Ex. 1 1.311.54 2.3 GPa 6.9 GPa 2.3 4.0 Ex. 2 1.27 1.54 1.5 GPa 6.6 GPa 2.1 4.3 Ex.3 1.33 1.58 2.9 GPa 7.5 GPa 2.4 4.0 Ex. 4 1.80 1.85 2.6 GPa 8.8 GPa 50.075.1 Ex. 5 1.33 1.45 2.4 GPa 6.4 GPa 2.4 3.7 Ex. 6 1.25 1.41 1.2 GPa 5.1GPa 1.9 3.0

[0261] Devices and capacitors having excellent interlayer insulatingfilm characteristics could be manufactured using the dielectric constantpatterns obtained in the above Examples 1 to 6.

[0262] Since the dielectric constant pattern formed by the method of thepresent invention has a sufficiently large dielectric constantdifference and this dielectric constant difference is stable to lightand heat, the dielectric constant pattern is extremely useful as aninterlayer insulating film material for use in optoelectronic anddisplay fields. The dielectric constant pattern of the present inventionis used as a material to be packaged, such as a capacitor.

1. A radiation sensitive dielectric constant changing compositioncomprising (A) a decomposable compound, (B) a nondecomposable compound,(C) a radiation sensitive decomposer and optionally (D) a stabilizer. 2.The composition of claim 1, wherein the dielectric constant of a portionexposed to radiation is 90% or less of the dielectric constant of anunexposed portion.
 3. The composition of claim 1 or 2, wherein thedecomposable compound (A) is an acid decomposable compound, thenondecomposable compound (B) is an acid nondecomposable compound, andthe radiation sensitive decomposer (C) is a radiation sensitive acidgenerator.
 4. The composition of claim 3, wherein the acid decomposablecompound (A) contains at least one of compounds having at least one ofstructures represented by the following formulas (1) to (6) and (10):

wherein R¹ is an alkylene group, alkylene-arylene-alkylene group orarylene group, and R² is an alkylene group, alkylene-arylene-alkylenegroup, arylene group, alkylsilylene group or alkylgermylene group,

wherein M is Si or Ge, R³ is an alkylene group,alkylene-arylene-alkylene group, arylene group, alkylsilylene group oralkylgermylene group, R⁴ is an oxygen atom, alkylene group,alkylene-arylene-alkylene group, arylene group or single bond, R⁵, R⁶,R⁷ and R⁸ are each independently a hydrogen atom, alkyl group, arylgroup, alkoxyl group or thioalkyl group, and m is an integer of 0 to 2,

wherein R⁹ and R¹⁰ are each independently an alkylene group,alkylene-arylene-alkylene group, arylene group, alkylsilylene group oralkylgermylene group,

wherein R¹¹ is an oxyalkylene group or single bond, and R¹² is ahydrogen atom, alkyl group, alkylene-arylene-alkylene group or arylgroup,

wherein R¹³ is a hydrogen atom, alkyl group or aryl group,

wherein R¹⁴ is an alkylene group or a structure represented by thefollowing formula (7), (8) or (9),

wherein R¹⁵, R¹⁶, R¹⁷ and R¹⁸ are each independently a hydrogen atom,chain alkyl group having 1 to 6 carbon atoms, chlorine atom, bromineatom, iodine atom, hydroxyl group, mercapto group, carboxyl group,alkoxyl group having 1 to 6 carbon atoms, alkylthio group having 1 to 6carbon atoms, haloalkyl group having 1 to 6 carbon atoms, haloalkoxylgroup having 1 to 6 carbon atoms, haloalkylthio group having 1 to 6carbon atoms, hydroxyalkyl group having 1 to 6 carbon atoms,mercaptoalkyl group having 1 to 6 carbon atoms, hydroxyalkoxyl grouphaving 1 to 6 carbon atoms, mercaptoalkylthio group having 1 to 6 carbonatoms, aryl group having 6 to 10 carbon atoms or aralkyl group having 7to 11 carbon atoms, —O—R¹⁹—O—  (8) wherein R¹⁹ is an alkylene group,—NH—R²⁰—NH—  (9) wherein R²⁰ is an alkylene group,

wherein R²¹ is an alkylene group, alkylene-arylene-alkylene group orarylene group.
 5. The composition of claim 1 or 2, wherein the aciddecomposable compound (A) is at least one compound selected from thegroup consisting of (i) a phenolic resin having at least two phenolichydroxyl groups and at least two phenyl groups in the molecule, at leastone of the phenolic hydroxyl groups forming anaphthoquinonediazidosulfonyl ester group, (ii) a novolak resin havingat least one phenolic hydroxyl group forming anaphthoquinonediazidosulfonyl ester group, (iii) a phenolic resin havingat least two phenolic hydroxyl groups and at least two phenyl group inthe molecule, at least one of the phenolic hydroxyl groups beingprotected by an acid decomposable protective group, (iv) a novolak resinhaving at least one phenolic hydroxyl group protected by an aciddecomposable protective group, and (v) a carboxyl group-containing resinhaving at least one carboxyl group protected by an acid decomposableprotective group.
 6. The composition of any one of claims 1 to 3,wherein the decomposable compound (A) is a base decomposable compound,the nondecomposable compound (B) is a base nondecomposable compound, andthe radiation sensitive decomposer (C) is a radiation sensitive basegenerator.
 7. The composition of claim 6, wherein the decomposablecompound (A) contains at least one of compounds having at least one ofstructures represented by the following formulas (11) to (13) and (14):

wherein R²² is an alkylene group, aralkylene group or arylene group, R²³is an alkylene group, aralkylene group, arylene group,alkylene-arylene-alkylene group, alkylsilylene group or alkylgermylenegroup, R²⁴, R²⁵, R²⁶ and R²⁷ are each independently a hydrogen atom,alkyl group, aryl group, alkoxyl group or thioalkyl group, and i and jare each independently 0 or 1,

wherein R²⁸ is an alkylene group, aralkylene group or arylene group, andR²⁹ is an alkylene group, aralkylene group, arylene group,alkylene-arylene-alkylene group, alkylsilylene group or alkylgermylenegroup,

wherein R³⁰ and R³¹ are each independently an alkylene group, aralkylenegroup, arylene group, alkylene-arylene-alkylene group, alkylsilylenegroup or alkylgermylene group,

wherein R³² and R³³ are each independently an alkylene group, aralkylenegroup, arylene group, alkylene-arylene-alkylene group, alkylsilylenegroup or alkylgermylene group.
 8. The composition of any one of claims 1to 7, wherein the stabilizer (D) is at least one selected from the groupconsisting of an amino compound, epoxy compound, thiirane compound,oxetane compound, alkoxymethyl melamine compound, alkoxymethylglycoluril compound, alkoxymethyl benzoguanamine compound, alkoxymethylurea compound, isocyanate compound, cyanate compound, oxazolinecompound, oxazine compound and silyl compound.
 9. The composition ofclaim 1 which comprises the stabilizer (D) and further comprises acatalyst for a reaction between the decomposable compound (A) and thestabilizer (D).
 10. A method of forming a dielectric constant pattern,comprising the steps of exposing a radiation sensitive dielectricconstant changing composition comprising (A) a decomposable compound,(B) a nondecomposable compound, (C) a radiation sensitive decomposer and(D) a stabilizer to radiation through a pattern mask and heating it toreact the stabilizer (D) with the decomposable compound (A) in anunexposed portion.
 11. The method of claim 10, wherein the dielectricconstant pattern consists of an exposed portion having a porosity of 10to 99.9% and an unexposed portion having substantially no pore.
 12. Amethod of forming a dielectric constant pattern, comprising the steps ofexposing a dielectric constant changing material comprising (A) adecomposable compound, (B) a nondecomposable compound and (C) aradiation sensitive decomposer to radiation through a pattern mask andtreating it with (D) a stabilizer to react the stabilizer (D) with thedecomposable compound (A) in an unexposed portion.
 13. The method ofclaim 12, wherein the dielectric constant pattern consists of an exposedportion having a porosity of 10 to 99.9% and an unexposed portion havingsubstantially no pore.
 14. A method of forming a dielectric constantpattern, comprising the steps of exposing a dielectric constant changingmaterial comprising (A) a decomposable compound, (B) a nondecomposablecompound and (C) a radiation sensitive, decomposer to radiation througha pattern mask and heating it to decompose the decomposable compound inan unexposed portion.
 15. The method of claim 14, wherein the dielectricconstant pattern consists of an exposed portion having a porosity of 10to 99.9% and an unexposed portion having substantially no pore.
 16. Adielectric constant pattern formed by the method of claim 10, 12 or 14.17. The dielectric constant pattern of claim 16 which consists of afirst region having a porosity of 10 to 99.9% and a second region havingsubstantially no pore and a higher dielectric constant than thedielectric constant of the first region.
 18. The dielectric constantpattern of claim 17, wherein the first region shows a lower elasticmodulus than the second region.
 19. A device having a dielectricconstant pattern formed by the method of claim 10, 12 or
 14. 20. Thedevice of claim 19 which consists of a first region having a porosity of10 to 99.9% and a second region having substantially no pore and ahigher dielectric constant than the dielectric constant of the firstregion.
 21. The device of claim 20, wherein the first region shows alower elastic modulus than the second region.